Surface treatment agent

ABSTRACT

wherein: each of the symbols are as defined herein. A content of the fluorine containing oil having a molecular weight of 2.0 or more times higher than the number average molecular weight of the fluorine-containing oils among the fluorine containing oil of the formula (O) is 10 mol % or less.

TECHNICAL FIELD

The present invention relates to a surface-treating agent, specifically,the surface-treating agent comprising a perfluoro(poly)ether groupcontaining silane compound and the fluorine containing oil.

BACKGROUND ART

A certain fluorine-containing silane compound is known to be able toprovide excellent water-repellency, oil-repellency, antifoulingproperty, or the like when it is used in a surface treatment of a basematerial. A layer (hereinafter, referred to as a “surface-treatinglayer”) formed from a surface-treating agent comprising afluorine-containing silane compound is applied to various base materialssuch as a glass, a plastic, a fiber and a building material as aso-called functional thin film.

As such fluorine-containing silane compound, a perfluoropolyether groupcontaining silane compound which has a perfluoropolyether group in itsmain molecular chain and a hydrolyzable group bonding to a Si atom inits molecular terminal or terminal portion is known. For example, PatentDocuments 1 and 2 disclose a perfluoropolyether group containing silanecompound having a hydrolyzable group bonding to a Si atom in itsmolecular terminal or terminal portion.

PRIOR ART DOCUMENT Patent Document

Patent Document 1: International Publication No. 97/07155

Patent Document 2: JP 2008-534696 A

Patent Document 3: International Publication No. 2014/163057

SUMMARY OF THE INVENTION Problem to be Solved by the Invention

The layer formed from the surface-treating agent containing theperfluoropolyether group containing silane compound has been suitablyused in an optical member such as glasses, a touch panel or the likewhich is required to have light permeability or transparency since itcan exert functions such as water-repellency, oil-repellency,antifouling property even in form of a thin film. In particular, inthese applications, the high surface slip property is required in orderto easily wipe a fouling such as fingerprints and to provide excellenttactile feeling when a user operates by touching a display panel withhis finger. In addition, friction durability is required in order tomaintain the functions even when friction is repeatedly subjected.

It is known that the fluorine containing oil is added into the surfacetreating agent to provide the surface treating agent with the excellentsurface slip property (Patent Document 3). However, the inventors hasnoted that transparency of a surface-treating layer formed may bedecreased when the fluorine containing oil is added to the surfacetreating agent comprising the perfluoro(poly)ether group containingsilane compound.

An object of the present invention is to provide the surface treatingagent comprising a perfluoro(poly)ether group containing silane compoundwhich is able to form a layer having water-repellency, oil-repellencyand antifouling property, waterproof property as well as high frictiondurability, high surface slip property and high transparency.

Means to Solve the Problem

As a result of intensively studying, the inventors of the presentinvention have found that, in the surface treating agent comprising theperfluoro(poly)ether group containing silane compound and the fluorinecontaining oil, by decreasing high molecular weight fraction of thefluorine containing oil contained in the surface treating agent, asurface treating layer having high friction durability and high surfaceslip property can be formed with transparency being suppressed, and theinventors reach the present invention.

Therefore, according to the first aspect of the present invention, thereis provided a surface-treating agent comprising

(1) at least one perfluoro(poly)ether group containing silane compoundof any of the formulae (A1), (A2), (B1), (B2), (C1), (C2), (D1) and(D2):

wherein:

PFPE is each independently at each occurrence a group of the formula:

—(OC₄F₈)_(a)—(OC₃F₆)_(b)—(OC₂F₄)_(c)—(OCF₂)_(d)—

wherein a, b, c and d are each independently an integer of 0-200, thesum of a, b, c and d is at least one, and the occurrence order of therespective repeating units in parentheses with the subscript a, b, c ord is not limited in the formula;

Rf is each independently at each occurrence an alkyl group having 1-16carbon atoms which may be substituted by one or more fluorine atoms;

R¹ is each independently at each occurrence a hydroxyl group or ahydrolyzable group;

R² is each independently at each occurrence a hydrogen atom or an alkylgroup having 1-22 carbon atoms;

R¹¹ is each independently at each occurrence a hydrogen atom or ahalogen atom;

R¹² is each independently at each occurrence a hydrogen atom or a loweralkyl group;

n1 is, independently per a unit (—SiR_(n1)R² _(3−n1)), an integer of0-3;

at least one n1 is an integer of 1-3 in the formulae (A1), (A2), (B1)and (B2);

X¹ is each independently a single bond or a 2-10 valent organic group;

X² is each independently at each occurrence a single bond or a divalentorganic group;

t is each independently at each occurrence an integer of 1-10;

α is each independently an integer of 1-9;

α′ is each independently an integer of 1-9;

X⁵ is each independently a single bond or a 2-10 valent organic group;

β is each independently an integer of 1-9;

β′ is each independently an integer of 1-9;

X⁷ is each independently a single bond or a 2-10 valent organic group;

γ is each independently an integer of 1-9;

γ′ is each independently an integer of 1-9;

R^(a) is each independently at each occurrence —Z¹—SiR⁷¹ _(p1)R⁷²_(q1)R⁷³ _(r1);

Z¹ is each independently at each occurrence an oxygen atom or a divalentorganic group;

R⁷ is each independently at each occurrence R^(a);

R^(a′) has the same definition as that of R^(a);

in R^(a), the number of Si atoms which are straightly linked via the Zgroup is up to five;

R⁷² is each independently at each occurrence a hydroxyl group or ahydrolyzable group;

R⁷³ is each independently at each occurrence a hydrogen atom or a loweralkyl group;

p1 is each independently at each occurrence an integer of 0-3;

q1 is each independently at each occurrence an integer of 0-3;

r1 is each independently at each occurrence an integer of 0-3;

at least one q1 is an integer of 1-3 in the formula (C1) and (C2);

R^(b) is each independently at each occurrence a hydroxyl group or ahydrolyzable group;

R^(c) is each independently at each occurrence a hydrogen atom or alower alkyl group;

k1 is each independently at each occurrence an integer of 1-3;

l1 is each independently at each occurrence an integer of 0-2;

m1 is each independently at each occurrence an integer of 0-2;

the sum of k1, l1 and m1 is 3 in each unit in parentheses with thesubscript γ;

X⁹ is each independently a single bond or a 2-10 valent organic group;

δ is each independently an integer of 1-9;

δ′ is each independently an integer of 1-9;

R^(d) is each independently at each occurrence —Z²—CR⁸¹ _(p2)R⁸²_(q2)R⁸³ _(r2);

Z² is each independently at each occurrence an oxygen atom or a divalentorganic group;

R⁸¹ is each independently at each occurrence R^(d′);

R^(d′) has the same definition as that of R^(d);

in R^(d′), the number of C atoms which are straightly linked via the Z²group is up to five;

R⁸² is each independently at each occurrence —Y—SiR⁸⁵ _(n2)R⁸⁶ _(3−n2);

Y is each independently at each occurrence a divalent organic group;

R⁸⁵ is each independently at each occurrence a hydroxyl group or ahydrolyzable group;

R⁸⁶ is each independently at each occurrence a hydrogen atom or a loweralkyl group;

n2 is an integer of 1-3 independently per unit (—Y—SiR⁸⁵ _(n2)R⁸⁶_(3−n2));

in formulae (D1) and (D2), at least one n2 is an integer of 1-3;

R⁸³ is each independently at each occurrence a hydrogen atom or a loweralkyl group;

p² is each independently at each occurrence an integer of 0-3;

q2 is each independently at each occurrence an integer of 0-3;

r2 is each independently at each occurrence an integer of 0-3;

R^(e) is each independently at each occurrence —Y—SiR⁸⁵ _(n2)R⁸⁶ _(n2);

R^(f) is each independently at each occurrence a hydrogen atom or alower alkyl group;

k2 is each independently at each occurrence an integer of 0-3;

l2 is each independently at each occurrence an integer of 0-3; and

m2 is each independently at each occurrence an integer of 0-3;

in formulae (D1) and (D2), at least one q2 is 2 or 3, or at least one l2is 2 or 3; and

(2) a fluorine containing oil of the general formula (O):

Rf¹-PFPE′-Rf²  (O)

wherein:

R^(f1) is each independently at each occurrence a C₁₋₁₆ alkyl groupwhich may be substituted by one or more fluorine atoms;

Rf² is a C₁₋₁₆ alkyl group which may be substituted by one or morefluorine atoms, a fluorine atom or a hydrogen atom;

PFPE′ is —(OC₄F₈)_(a′)—(OC₃F₆)_(b′)—(OC₂F₄)_(c′)—(OCF₂)_(d′)—;

a′, b′, c′ and d′ are each independently an integer of 0 or more and 300or less, the sum of a′, b′, c′ and d′ is at least 1, and the occurrenceorder of the respective repeating units in parentheses with thesubscript a′, b′, c′ or d′ is not limited in the formula,

wherein a content of the fluorine containing oil having a molecularweight of 2.0 or more times higher than the number average molecularweight of the fluorine-containing oil among the fluorine containing oilof the formula (O) is 10 mol % or less.

Therefore, according to the second aspect of the present invention,there is provided a surface-treating agent comprising

(1) at least one perfluoro(poly)ether group containing silane compoundof any of the formulae (A1), (A2), (B1), (B2), (C1), (C2), (D1) and(D2):

wherein:

PFPE is each independently at each occurrence a group of the formula:

—(OC₄F₈)_(a)—(OC₃F₆)_(b)—(OC₂F₄)_(c)—(OCF₂)_(d)—

wherein a, b, c and d are each independently an integer of 0-200, thesum of a, b, c and d is at least one, and the occurrence order of therespective repeating units in parentheses with the subscript a, b, c ord is not limited in the formula;

Rf is each independently at each occurrence an alkyl group having 1-16carbon atoms which may be substituted by one or more fluorine atoms;

R¹ is each independently at each occurrence a hydroxyl group or ahydrolyzable group;

R² is each independently at each occurrence a hydrogen atom or an alkylgroup having 1-22 carbon atoms;

R¹¹ is each independently at each occurrence a hydrogen atom or ahalogen atom;

R¹² is each independently at each occurrence a hydrogen atom or a loweralkyl group;

n1 is, independently per a unit (—SiR_(n1)R² _(3−n1)), an integer of0-3;

at least one n1 is an integer of 1-3 in the formulae (A1), (A2), (B1)and (B2);

X¹ is each independently a single bond or a 2-10 valent organic group;

X² is each independently at each occurrence a single bond or a divalentorganic group;

t is each independently at each occurrence an integer of 1-10;

α is each independently an integer of 1-9;

α′ is each independently an integer of 1-9;

X⁵ is each independently a single bond or a 2-10 valent organic group;

β is each independently an integer of 1-9;

β′ is each independently an integer of 1-9;

X⁷ is each independently a single bond or a 2-10 valent organic group;

γ is each independently an integer of 1-9;

γ′ is each independently an integer of 1-9;

R^(a) is each independently at each occurrence —Z¹—SiR⁷¹ _(p1)R⁷²_(q1)R⁷³ _(r1);

Z¹ is each independently at each occurrence an oxygen atom or a divalentorganic group;

R⁷¹ is each independently at each occurrence R^(a);

R^(a′) has the same definition as that of R^(a);

in R^(a), the number of Si atoms which are straightly linked via the Zgroup is up to five;

R⁷² is each independently at each occurrence a hydroxyl group or ahydrolyzable group;

R⁷³ is each independently at each occurrence a hydrogen atom or a loweralkyl group;

p1 is each independently at each occurrence an integer of 0-3;

q1 is each independently at each occurrence an integer of 0-3;

r1 is each independently at each occurrence an integer of 0-3;

at least one q1 is an integer of 1-3 in the formula (C1) and (C2);

R^(b) is each independently at each occurrence a hydroxyl group or ahydrolyzable group;

R^(c) is each independently at each occurrence a hydrogen atom or alower alkyl group;

k1 is each independently at each occurrence an integer of 1-3;

l1 is each independently at each occurrence an integer of 0-2;

m1 is each independently at each occurrence an integer of 0-2;

the sum of k1, l1 and m1 is 3 in each unit in parentheses with thesubscript γ;

X⁹ is each independently a single bond or a 2-10 valent organic group;

δ is each independently an integer of 1-9;

δ′ is each independently an integer of 1-9;

R^(d) is each independently at each occurrence —Z²—CR⁸¹ _(p2)R⁸²_(q2)R⁸³ _(r2); Z² is each independently at each occurrence an oxygenatom or a divalent organic group;

R⁸¹ is each independently at each occurrence R^(d′);

R^(d′) has the same definition as that of R^(d);

in R^(d), the number of C atoms which are straightly linked via the Z²group is up to five;

R⁸² is each independently at each occurrence —Y—SiR⁸⁵ _(n2)R⁸⁶ _(3−n2);

Y is each independently at each occurrence a divalent organic group;

R⁸⁵ is each independently at each occurrence a hydroxyl group or ahydrolyzable group;

R⁸⁶ is each independently at each occurrence a hydrogen atom or a loweralkyl group;

n2 is an integer of 1-3 independently per unit (—Y—SiR⁸⁵ _(n2)R⁸⁶_(3−n2));

in formulae (D1) and (D2), at least one n2 is an integer of 1-3;

R⁸³ is each independently at each occurrence a hydrogen atom or a loweralkyl group;

p² is each independently at each occurrence an integer of 0-3;

q2 is each independently at each occurrence an integer of 0-3;

r2 is each independently at each occurrence an integer of 0-3;

R^(e) is each independently at each occurrence —Y—SiR⁸⁵ _(n2)R⁸⁶ _(n2);

R^(f) is each independently at each occurrence a hydrogen atom or alower alkyl group;

k2 is each independently at each occurrence an integer of 0-3;

l2 is each independently at each occurrence an integer of 0-3; and

m2 is each independently at each occurrence an integer of 0-3;

in formulae (D1) and (D2), at least one q2 is 2 or 3, or at least one l2is 2 or 3; and

(2) a fluorine containing oil of the general formula (O):

Rf¹-PFPE′-Rf²  (O)

wherein:

Rf¹ is each independently at each occurrence a C₁₋₁₆ alkyl group whichmay be substituted by one or more fluorine atoms;

Rf² is a C₁₋₁₆ alkyl group which may be substituted by one or morefluorine atoms, a fluorine atom or a hydrogen atom;

PFPE′ is —(OC₄F₈)_(a′)—(OC₃F₆)_(b′)—(OC₂F₄)_(c′)—(OCF₂)_(d′)—;

a′, b′, c′ and d′ are each independently an integer of 0 or more and 300or less, the sum of a′, b′, c′ and d′ is at least 1, and the occurrenceorder of the respective repeating units in parentheses with thesubscript a′, b′, c′ or d′ is not limited in the formula,

wherein a content of the fluorine containing oil having a molecularweight of 5,000 or more in the fluorine containing oil of the formula(O) is 10 mol % or less.

According to the third aspect of the present invention, there isprovided a pellet comprising the surface-treating agent described above.

According to the fourth aspect of the present invention, there isprovided an article comprising a base material and a layer which isformed on a surface of the base material from the surface-treating agentdescribed above.

Effect of the Invention

According to the present invention, there is provided a novel surfacetreating agent comprising the perfluoro(poly)ether group containingsilane compound and a fluorine containing silane. By using the surfacetreating agent, a layer is able to be formed, which haswater-repellency, oil-repellency, and antifouling property as well ashigh transparency, high friction durability and high surface slipproperty can be formed.

Embodiments to Carry Out the Invention

Hereinafter, the compound of the present invention will be described.

A “hydrocarbon group” as used herein represents a group containing acarbon atom and a hydrogen atom which is obtained by removing a hydrogenatom from a hydrocarbon. Examples of the hydrocarbon group include, butare not particularly limited to, a hydrocarbon group having 1-20 carbonatoms which may be substituted with one or more substituents, forexample, an aliphatic hydrocarbon group, an aromatic hydrocarbon group,and the like. The “aliphatic hydrocarbon group” may be straight,branched or cyclic, and may be saturated or unsaturated. The hydrocarbongroup may contain one or more ring structures. It is noted that thehydrocarbon group may have one or more N, O, S, Si, amide, sulfonyl,siloxane, carbonyl, carbonyloxy, or the like at its end or in itsmolecular chain.

As used herein, examples of the substituent of the “hydrocarbon group”include, but are not particularly limited to, for example a halogenatom; and a C₁₋₆ alkyl group, a C₂₋₆ alkenyl group, a C₂₋₆ alkynylgroup, a C₃₋₁₀ cycloalkyl group, a C₃₋₁₀ unsaturated cycloalkyl group, a5-10 membered heterocyclyl group, a 5-10 membered unsaturatedheterocyclyl group, a C₆₋₁₀ aryl group, a 5-10 membered heteroarylgroup, and the like, which may be substituted by one or more halogenatoms.

A “2-10 valent organic group” as used herein represents a 2-10 valentgroup containing a carbon atom. Examples of the 2-10 valent organicgroup include, but are not particularly limited to, a 2-10 valent groupobtained by removing 1-9 hydrogen atoms from a hydrocarbon group. Forexample, examples of the divalent organic group include, but are notparticularly limited to, a divalent group obtained by removing onehydrogen atom from a hydrocarbon group from a hydrocarbon group.

The surface treating agent of the present invention comprises (1) aperfluoro(poly)ether group containing silane compound and (2) a fluorinecontaining oil.

The perfluoro(poly) ether group containing silane compound used in thepresent invention is at least one perfluoro(poly)ether group containingsilane compound of any of the general formulae (A1), (A2), (B1), (B2),(C1), (C2), (D1) and (D2).

Hereinafter, the compound of the formulae (A1), (A2), (B1), (B2), (C1),(C2), (D1) and (D2) described above are described.

In the formula described above, PFPE is each independently—(OC₄F₈)_(a)—(OC₃F₆)_(b)—(OC₂F₄)_(c)—(OCF₂)_(d)—, and corresponds to aperfluoro(poly)ether group. Herein, a, b, c and d are each independently0 or an integer of 1 or more. The sum of a, b, c and d is 1 or more.Preferably, a, b, c and d are each independently an integer of 0 or moreand 200 or less, for example an integer of 1 or more and 200 or less,more preferably each independently an integer of 0 or more and 100 orless. The sum of a, b, c and d is preferably 5 or more, more preferably10 or more, for example 10 or more and 100 or less. The occurrence orderof the respective repeating units in parentheses with the subscript a,b, c or d is not limited in the formula. Among these repeating units,the —(OC₄F₈)— group may be any of —(OCF₂CF₂CF₂CF₂)—, —(OCF(CF₃)CF₂CF₂)—,—(OCF₂CF(CF₃)CF₂)—, —(OCF₂CF₂CF(CF₃))—, —(OC(CF₃)₂CF₂)—,—(OCF₂C(CF₃)₂)—, —(OCF(CF₃)CF(CF₃))—, —(OCF(C₂F₅)CF₂)— and—(OCF₂CF(C₂F))—, preferably —(OCF₂CF₂CF₂CF₂)—. The —(OC₃F₆)— group maybe any of —(OCF₂CF₂CF₂)—, —(OCF(CF₃)CF₂)— and —(OCF₂CF(CF₃))—,preferably —(OCF₂CF₂CF₂)—. The —(OC₂F₄)— group may be any of —(OCF₂CF₂)—and —(OCF(CF₃))—, preferably —(OCF₂CF₂)—.

In one embodiment, PFPE is —(OC₃F₆)_(b)— wherein b is an integer of 1 ormore and 200 or less, preferably 5 or more and 200 or less, morepreferably 10 or more and 200 or less, preferably —(OCF₂CF₂CF₂)_(b)—wherein b is an integer of 1 or more and 200 or less, preferably 5 ormore and 200 or less, more preferably 10 or more and 200 or less, or—(OCF(CF₃)CF₂)_(b)— wherein b is an integer of 1 or more and 200 orless, preferably 5 or more and 200 or less, more preferably 10 or moreand 200 or less, more preferably —(OCF₂CF₂CF₂)_(b)— wherein b is aninteger of 1 or more and 200 or less, preferably 5 or more and 200 orless, more preferably 10 or more and 200 or less.

In another embodiment, PFPE is—(OC₄F₈)_(a)—(OC₃F₆)_(b)—(OC₂F₄)_(c)—(OCF₂)_(d)— wherein a and b areeach independently an integer of 0 or more and 30 or less, c and d areeach independently an integer of 1 or more and 200 or less, preferably 5or more and 200 or less, more preferably 10 or more and 200 or less, andthe occurrence order of the respective repeating units in parentheseswith the subscript a, b, c or d is not limited in the formula;preferably—(OCF₂CF₂CF₂CF₂)_(a)—(OCF₂CF₂CF₂)_(b)—(OCF₂CF₂)_(c)—(OCF₂)_(d)—. In oneembodiment, PFPE may be —(OC₂F₄)_(c)—(OCF₂)_(d)— wherein c and d areeach independently an integer of 1 or more and 200 or less, preferably 5or more and 200 or less, more preferably 10 or more and 200 or less, andthe occurrence order of the respective repeating units in parentheseswith the subscript c or d is not limited in the formula.

In further another embodiment, PFPE is a group of —(R⁷-R⁸)_(f)—. In theformula, R¹ is OCF₂ or OC₂F₄, preferably OC₂F₄. That is, preferably PFPEis a group of —(OC₂F₄—R⁸)_(f)—. In the formula, R⁸ is a group selectedfrom OC_(Z)F₄, OC₃F₆ and OC₄F₈, or a combination of 2 or 3 groupsindependently selected from these groups. Examples of the combination of2 or 3 groups independently selected from OC₂F₄, OC₃F₆ and OC₄F₈include, but not limited to, for example, —OC₂F₄OC₃F₆—, —OC₂F₄OC₄F₈—,—OC₃F₆OC₂F₄—, —OC₃F₆OC₃F₆—, —OC₃F₆OC₄F₈—, —OC₄F₈OC₄F₈—, —OC₄F₈OC₃F₆—,—OC₄F₈OC_F₄—, —OC₂F₄OC₂F₄OC₃F₆—, —OC₂F₄OC₄F₄OC₄F₈—, —OC₂F₄OC₃F₆OC₂F₄—,—OC₂F₄OC₃F₆OC₃F₆—, —OC₂F₄OC₄F OC_(Z) F₄—, —OC₃F₆OC₂F₄OC₂F₄—,—OC₃F₆OC₂F₄OC₃F₆—, —OC₃F₆OC₃F₆OCF₄—, —OC₄F₄OC₂F₄OC₂F₄—, and the like. fis an integer of 2-100, preferably an integer of 2-50. In theabove-mentioned formula, OC₂F₄, OC₃F₆ and OC₄F₈ may be straight orbranched, preferably straight. In this embodiment, PFPE is preferably—(OC₂F₄—OC₃F₆)_(f)— or —(OC₂F₄—OC₄F₈)_(f)—.

In the formula, Rf is an alkyl group having 1-16 carbon atoms which maybe substituted by one or more fluorine atoms.

The “alkyl group having 1-16 carbon atoms” in the alkyl having 1-16carbon atoms which may be substituted by one or more fluorine atoms maybe straight or branched, and preferably is a straight or branched alkylgroup having 1-6 carbon atoms, in particular 1-3 carbon atoms, morepreferably a straight alkyl group having 1-3 carbon atoms.

Rf is preferably an alkyl having 1-16 carbon atoms substituted by one ormore fluorine atoms, more preferably a CF₂H—C₁₋₁₅ fluoroalkylene group,more preferably a perfluoroalkyl group having 1-16 carbon atoms.

The perfluoroalkyl group having 1-16 carbon atoms may be straight orbranched, and preferably is a straight or branched perfluoroalkyl grouphaving 1-6 carbon atoms, in particular 1-3 carbon atoms, more preferablya straight perfluoroalkyl group having 1-3 carbon atoms, specifically—CF₃, —CF₂CF₃ or —CF₂CF₂CF₃.

In the formula, R¹ is each independently at each occurrence a hydroxylgroup or a hydrolyzable group.

In the formula, R² is each independently at each occurrence a hydrogenatom or an alkyl group having 1-22 carbon atoms preferably an alkylgroup having 1-4 carbon atoms.

The “hydrolyzable group” as used herein represents a group which is ableto be removed from a backbone of a compound by a hydrolysis reaction.Examples of the hydrolyzable group include —OR, —OCOR, —O—N═CR₂, —NR₂,—NHR, halogen (wherein R is a substituted or non-substituted alkyl grouphaving 1-4 carbon atoms), preferably —OR (i.e. an alkoxy group).Examples of R include a non-substituted alkyl group such as a methylgroup, an ethyl group, a propyl group, an isopropyl group, an n-butylgroup, an isobutyl group; and a substituted alkyl group such as achloromethyl group. Among them, an alkyl group, in particular anon-substituted alkyl group is preferable, a methyl group or an ethylgroup is more preferable. The hydroxyl group may be, but is notparticularly limited to, a group generated by hydrolysis of ahydrolyzable group.

In the formula, R¹¹ is each independently at each occurrence a hydrogenatom or a halogen atom. The halogen atom is preferably an iodine atom, achlorine atom, a fluorine atom, more preferably a fluorine atom.

In the formula, R¹² is each independently at each occurrence a hydrogenatom or a lower alkyl group. The lower alkyl group is preferably analkyl group having 1-20 carbon atoms, more preferably an alkyl grouphaving 1-6 carbon atoms, for example a methyl group, an ethyl group, anpropyl group, or the like.

In the formula, n1 is, independently per a unit (—SiR¹ _(n1)R² _(3−n1)),an integer of 0-3, preferably 0-2, more preferably 0. All of n1 are notsimultaneously 0 in the formula. In other words, at least one R¹ ispresent in the formula.

In the formula, X¹ is each independently a single bond or a 2-10 valentorganic group. X¹ is recognized to be a linker which connects between aperfluoropolyether moiety (i.e., an Rf-PFPE moiety or -PFPE- moiety)providing mainly water-repellency, surface slip property and the likeand a silane moiety (i.e., a group in parentheses with the subscript a)providing an ability to bind to a base material in the compound of theformula (A1) and (A2) Therefore, X¹ may be any organic group as long asthe compound of the formula (A1) and (A2) can stably exist.

In the formula, a is an integer of 1-9, and α′ is an integer of 1-9. αand α′ may be varied depending on the valence number of the X¹ group. Inthe formula (A1), the sum of a and α′ is the valence number of X¹. Forexample, when X¹ is a 10 valent organic group, the sum of α and α′ is10, for example, a is 9 and α′ is 1, a is 5 and α′ is 5, or α is 1 andα′ is 9. When X¹ is a divalent organic group, α and α′ are 1. In theformula (A2), a is a value obtained by subtracting 1 from the valencenumber of X¹.

X¹ is preferably a 2-7 valent, more preferably 2-4 valent, morepreferably a divalent organic group.

In one embodiment, X¹ is a 2-4 valent organic group, a is 1-3, and α′ is1.

In another embodiment, X¹ is a divalent organic group, α is 1, and α′is 1. In this case, the formulae (A1) and (A2) are represented by thefollowing formulae (A1′) and (A2′).

Examples of X¹ include, but are not particularly limited to, for examplea divalent group of the following formula:

—(R³¹)_(p′)—(X^(a))_(q′)—

wherein:

R³¹ is each independently at each occurrence a single bond, —(CH₂)_(s)′—or an o-, m- or p-phenylene group, preferably —(CH₂)_(s′)—,

s′ is an integer of 1-20, preferably an integer of 1-6, more preferablyan integer of 1-3, further more preferably 1 or 2,

X^(a) is each independently at each occurrence —(X^(b))_(1′),

X^(b) is each independently at each occurrence a group selected from thegroup consisting of —O—, —S—, an o-, m- or p-phenylene group, —C(O)O—,—Si(R³³)₂—, —(Si(R³³)₂O)_(m′)—Si(R³³)₂—, —CONR³⁴—, —O—CONR³⁴—, —NR³⁴—and —(CH₂)_(n′)—,

R³³ is each independently at each occurrence a phenyl group, a C₁₋₆alkyl group or a C₁₋₆ alkoxy group, preferably a phenyl group or a C₁₋₆alkyl group, more preferably a methyl group,

R³⁴ is each independently at each occurrence a hydrogen atom, a phenylgroup or a C₁₋₆ alkyl group (preferably a methyl group),

m′ is each independently at each occurrence an integer of 1-100,preferably an integer of 1-20,

n′ is each independently at each occurrence an integer of 1-20,preferably an integer of 1-6, more preferably an integer of 1-3,

l′ is an integer of 1-10, preferably an integer of 1-5, more preferablyan integer of 1-3,

p′ is 0 1 or 2,

q′ is 0 or 1, and

at least one of p′ and q′ is 1, and the occurrence order of therespective repeating units in parentheses with the subscript p′ or q′ isnot limited in the formula. Here, R³¹ and X^(a) (typically, a hydrogenatom in R³¹ and X^(a)) may be substituted with one or more substituentsselected from a fluorine atom, a C₁₋₃ alkyl group and a C₁₋₃ fluoroalkylgroup.

Preferably, X¹ is —(R³¹)_(p′)—(X^(a))_(q′)—R³²—. R³² is a single bond,—(CH₂)_(t′)— or an o-, m- or p-phenylene group, preferably —(CH₂)_(t′)—.t′ is an integer of 1-20, preferably an integer of 2-6, more preferablyan integer of 2-3. Here, R³² (typically, a hydrogen atom in R³²) may besubstituted with one or more substituents from a fluorine atom, a C₁₋₃alkyl group and a C₁₋₃ fluoroalkyl group.

Preferably, X¹ may be

a C₁₋₂₀ alkylene group,—R³¹—X^(c)—R³²—, or—X^(d)—R³²—wherein R³¹ and R³² are as defined above.

More preferably, X¹ may be

a C₁₋₂₀ alkylene group,—(CH₂)_(s′)—X^(c)—,—(CH₂)_(s′)—X^(c)—(CH₂)_(t′)—,

—X^(d)—, or

—X^(d)—(CH₂)_(t′)—,wherein s′ and t′ are as defined above.

In the formula, X^(c) is

—O—, —S—, —C(O)O—, —CONR³⁴—, —O—CONR³⁴—,

—Si(R³³)₂—,—(Si(R³³)₂O)_(m′)—Si(R³³)₂—,—O—(CH₂)_(u′)—(Si(R³³)₂O)_(m′)—Si(R³³)₂—,—O—(CH₂)_(u′)—Si(R³³)₂—O—Si(R³³)₂—CH₂CH₂—Si(R³³)₂—O—Si(R³³)₂—,—O—(CH₂)_(u′)—Si(OCH₃)₂OSi(OCH₃)₂—,—CONR³⁴—(CH₂)_(u′)—(Si(R³³)₂O)_(m′)—Si(R³³)₂—,—CONR³⁴—(CH₂)_(u′)—N(R³⁴)—, or—CONR³⁴-(o-, m- or p-phenylene)-Si(R³³)₂—,wherein R³³, R³⁴ and m′ are as defined above, and

u′ is an integer of 1-20, preferably an integer of 2-6, more preferablyan integer of 2-3. X^(c) is preferably —O—.

In the formula, X^(d) is

—S—, —C(O)O—, —CONR³⁴—,

—CONR³⁴—(CH₂)_(u′)—(Si(R³³)₂O)_(m′)—Si(R³³)₂—,—CONR³⁴—(CH₂)_(u′)—N(R³⁴)—, or—CONR³⁴-(o-, m- or p-phenylene)-Si(R³³)₂—wherein each of symbols is as defined above.

more preferably, X¹ is

a C₁₋₂₀ alkylene group,—(CH₂)_(s′)—X^(c)—(CH₂)_(t′)—, or—X^(d)—(CH₂)_(t′)—wherein each of symbols is as defined above.

Further more preferably, X¹ is

a C₁₋₂₀ alkylene group,—(CH₂)_(s′)—O—(CH₂)_(t′)—,—(CH₂)_(s′)—(Si(R³³)₂)^(m′)—Si(R³³)₂—(CH₂)_(t′)—,—(CH₂)_(s′)—O—(CH₂)_(u′)—(Si(R³³)₂O)_(m′)—Si(R³³)₂—(CH₂)_(t′)—, or—(CH₂)_(s′)—O—(CH₂)_(t′)—Si(R³³)₂—(CH₂)_(u′)—Si(R³³)₂—(C_(v)H_(2v))—wherein R¹³, m′, s′, t′ and u′ are as defined above, and v is an integerof 1-20, preferably an integer of 2-6, more preferably an integer of2-3.

In the formula, —(C_(v)H_(2v))— may be straight or branched, forexample, may be, for example, —CH₂CH₂—, —CH₂CH₂CH₂—, —CH(CH₃)—,—CH(CH₃)CH₂—.

X¹ may be substituted with one or more substituents selected from afluorine atom, a C₁₋₃ alkyl group and a C₁₋₃ fluoroalkyl group(preferably, a C₁₋₃ perfluoroalkyl group).

In another embodiment, examples of X¹ include, for example, thefollowing groups:

wherein R⁴¹ is each independently a hydrogen atom, a phenyl group, analkyl group having 1-6 carbon atoms, or a C₁₋₆ alkoxy group, preferablya methyl group;

D is a group selected from:

—CH₂O(CH₂)₂—,—CH₂O(CH₂)₃—,—CF₂O(CH₂)₃—,—(CH₂)₂—,—(CH₂)₃—,—(CH₂)₄—,

—CONH—(CH₂)—,

—CONH—(CH₂)₂—,—CONH—(CH₂)₃—,—CON(CH₃)—(CH)₃—,—CON(Ph)-(CH₂)₃— wherein Ph is a phenyl group, and

wherein R⁴² is each independently a hydrogen atom, a C₁₋₆ alkyl group,or a C₁₋₆ alkoxy group, preferably a methyl group or a methoxy group,more preferably a methyl group,

E is —(CH₂)_(n)— wherein n is an integer of 2-6, and D binds to PFPE ofthe main backbone, and E binds to a group opposite to PFPE.

Specific examples of X¹ include, for example:

—CH₂O(CH₂)₂—,—CH₂O(CH₂)₃—,—CH₂O(CH₂)₆—,—CH₂O(CH₂)₃Si(CH₃)₂OSi(CH₃)₂(CH₂)₂—,—CH₂O(CH₂)₃Si(CH₃)₂OSi(CH₃)₂OSi(CH₃)₂(CH₂)₂—,—CH₂O(CH₂)₃Si(CH₃)₂O(Si(CH₃)₂O)₂Si(CH₃)₂(CH₂)₂—,—CH₂O(CH₂)₃Si(CH₃)₂O(Si(CH₃)₂O)₃Si(CH₃)₂(CH₂)₂—,—CH₂O(CH₂)₃Si(CH₃)₂O(Si(CH₃)₂O)₁₀Si(CH₃)₂(CH₂)₂—,—CH₂O(CH₂)₃Si(CH₃)₂O(Si(CH₃)₂O)₂₀Si(CH₃)₂(CH₂)₂—,—CH₂OCF₂CHFOCF₂—,—CH₂OCF₂CHFOCF₂CF₂—,—CH₂OCF₂CHFOCF₂CF₂CF₂—,—CH₂OCH₂CF₂CF₂OCF₂—,—CH₂OCH₂CF₂CF₂OCF₂CF₂—,—CH₂OCH₂CF₂CF₂OCF₂CF₂CF₂—,—CH₂OCH₂CF₂CF₂OCF(CF₃)CF₂OCF₂—,—CH₂OCH₂CF₂CF₂OCF(CF₃)CF₂OCF₂CF₂—,—CH₂OCH₂CF₂CF₂OCF(CF₃)CF₂OCF₂CF₂CF₂—,—CH₂OCH₂CHFCF₂OCF₂—,—CH₂OCH₂CHFCF₂OCF₂CF₂—,—CH₂OCH₂CHFCF₂OCF₂CF₂CF₂—,—CH₂OCH₂CHFCF₂OCF(CF₃)CF₂OCF₂—,—CH₂OCH₂CHFCF₂OCF(CF₃)CF₂OCF₂CF₂—,—CH₂OCH₂CHFCF₂OCF(CF₃)CF₂OCF₂CF₂CF₂—,—CH₂OCH₂(CH₂)₇CH₂Si(OCH₃)₂OSi(OCH₃)₂(CH₂)₂Si(OCH₃)₂OSi(OCH₃)₂(CH₂)₂—,—CH₂OCH₂CH₂CH₂Si(OCH₃)₂OSi(OCH₃)₂(CH₂)₃—,—CH₂OCH₂CH₂CH₂Si(OCH₂CH₃)₂OSi(OCH₂CH₃)₂(CH₂)₂—,—CH₂OCH₂CH₂CH₂Si(OCH₃)₂OSi(OCH₃)₂(CH₂)₂—,—CH₂OCH₂CH₂CH₂Si(OCH₂CH₃)₂OSi(OCH₂CH₃)₂(CH₂)₂—,—(CH₂)₂—,—(CH₂)₃—,—(CH₂)₄—,—(CH₂)₅—,—(CH₂)₆—,—(CH₂)₂—Si(CH₃)₂—(CH₂)₂—

—CONH—(CH₂)—,

—CONH—(CH₂)₂—,—CONH—(CH₂)₃—,—CON(CH₃)—(CH₂)₃—,—CON(Ph)-(CH₂)₃— wherein Ph is phenyl,—CONH—(CH₂)₆—,—CON(CH₃)—(CH₂)₆—,—CON(Ph)-(CH₂)₆— wherein Ph is phenyl,—CONH—(CH₂)₂NH(CH₂)₃—,—CONH—(CH₂)₆NH(CH₂)₃—,—CH₂O—CONH—(CH₂)₃—,—CH₂O—CONH—(CH₂)₆—,—S—(CH₂)₃—,—(CH₂)₂S(CH₂)₃—,—CONH—(CH₂)₃Si(CH₃)₂OSi(CH₃)₂(CH₂)₂—,—CONH—(CH₂)₃Si(CH₃)₂OSi(CH₃)₂OSi(CH₃)₂(CH₂)₂—,—CONH—(CH₂)₃Si(CH₃)₂O(Si(CH₃)₂O)₂Si(CH₃)₂(CH₂)₂—,—CONH—(CH₂)₃Si(CH₃)₂O(Si(CH₃)₂O)₃Si(CH₃)₂(CH₂)₂—,—CONH—(CH₂)₃Si(CH₃)₂O(Si(CH₃)₂O)₁₀Si(CH₃)₂(CH₂)₂—,—CONH—(CH₂)₃Si(CH₃)₂O(Si(CH₃)₂)₂₀Si(CH₃)₂(CH₂)₂——C(O)O—(CH₂)₃—,—C(O)O—(CH₂)₃—Si(CH₃)₂—(CH₂)₂—Si(CH₃)₂—(CH₂)₂—,—CH₂—O—(CH₂)₃—Si(CH₃)₂—(CH₂)₂—Si(CH₃)₂—(CH₂)₂—,—CH₂—O—(CH₂)₃—Si(CH₃)₂—(CH₂)₂—Si(CH₃)₂—CH(CH₃)—CH₂—,

—OCH₂—,

—O(CH₂)₃—,

—OCFHCF₂—,

In another preferable embodiment, X¹ is a group of the formula:—(R¹⁶)_(x)—(CFR¹⁷)_(y)—(CH₂)_(z)—. In the formula, x, y and z are eachindependently an integer of 0-10, the sum of x, y and z is 1 or more,and the occurrence order of the respective repeating units inparentheses is not limited in the formula.

In the formula, R¹⁶ is each independently at each occurrence an oxygenatom, phenylene, carbazolylene, —NR²⁶— (wherein R²⁶ is a hydrogen atomor an organic group) or a divalent organic group. Preferably, R¹¹ is anoxygen atom or a divalent polar group.

Examples of the “divalent polar group” include, but are not particularlylimited to, —C(O)—, —C(═NR²⁷)—, and —C(O)NR²⁷— wherein R²⁷ is a hydrogenatom or a lower alkyl group. The “lower alkyl group” is, for example, analkyl group having 1-6 carbon atoms, for example, methyl, ethyl,n-propyl, which may be substituted by one or more fluorine atoms.

In the formula, R¹⁷ is each independently at each occurrence a hydrogenatom, a fluorine atom or a lower fluoroalkyl group, preferably afluorine atom. The “lower fluoroalkyl group” is, for example, preferablya fluoroalkyl group having 1-6 carbon atoms, preferably 1-3 carbonatoms, preferably a perfluoroalkyl group having 1-3 carbon atoms, morepreferably a trifluoromethyl group, and a pentafluoroethyl group,further preferably a trifluoromethyl group.

In this embodiment, X¹ is preferably is a group of the formula:—(O)_(x)—(CF₂)_(y)—(CH₂)_(z)— wherein x, y and z are as defined above,and the occurrence order of the respective repeating units inparentheses is not limited in the formula.

Examples of the group of the formula: —(O)_(x)—(CF₂)_(y)—(CH₂)_(z)—include, for example, —(O)_(x′)—(CH₂)_(z″)—O—[(CH₂)_(z′″)—O—]_(z″″), and—(O)_(x′)—(CF₂)_(y″)—(CH₂)_(z″)—O—[(CH₂)_(z′″)—O—]_(″″) wherein x′ is 0or 1, y″, z″ and z′″ are each independently an integer of 1-10, and z″″is 0 or 1. It is noted that these groups are attached to PFPE at itsleft side terminal.

In another preferable embodiment, X¹ is —O—CFR¹³—(CF₂)_(c)—.

R¹³ is each independently a fluorine atom or a lower fluoroalkyl group.The lower fluoroalkyl group is, for example, a fluoroalkyl group having1-3 carbon atoms, preferably a perfluoroalkyl group having 1-3 carbonatoms, more preferably a trifluoromethyl group, and a pentafluoroethylgroup, further preferably a trifluoromethyl group.

e is each independently 0 or 1.

In one embodiment, R¹³ is a fluorine atom, and e is 1.

In another embodiment, examples of X¹ include the following groups:

wherein R⁴¹ is each independently a hydrogen atom, a phenyl group, analkyl group having 1-6 carbon atoms, or a C₁₋₆ alkoxy group, preferablya methyl group;

in each X¹, some of T are a following group which binds to PFPE of themain backbone:

—CH₂O(CH₂)₂—,—CH₂O(CH₂)₃—,—CF₂O(CH)₃—,—(CH₂)₂—,—(CH₂)₃—,—(CH₂)₄—,

—CONH—(CH₂)—,

—CONH—(CH₂)₂—,—CONH—(CH₂)₃—,—CON(CH₃)—(CH₂)₃—,—CON(Ph)-(CH₂)₃— wherein Ph is phenyl, or

wherein R⁴² is each independently a hydrogen atom, a C₁₋₆ alkyl group,or a C₁₋₆ alkoxy group, preferably a methyl group or a methoxy group,more preferably a methyl group, some of the other T are —(CH₂)_(n)″—(wherein n″ is an integer of 2-6) attached to the group opposite to PFPEwhich is a molecular backbone (i.e., a carbon atom in the formulae (A1),(A2), (D1) and (D2), and a Si atom in the formulae (B1), (B2), (C1) and(C2)), and

the others T are each independently a methyl group, a phenyl group, or aC₁₋₆ alkoxy or a radical scavenger group or an ultraviolet ray absorbinggroup, if present.

The radical scavenger group is not limited as long as it can trap aradical generated by light irradiation, and includes, for example, aresidue of benzophenones, benzotriazoles, benzoic esters, phenylsalicylates, crotonic acids, malonic esters, organoacrylates, hinderedamines, hindered phenols, or triazines.

The ultraviolet ray absorbing group is not limited as long as it canabsorb an ultraviolet ray, and includes, for example, benzotriazoles,hydroxybenzophenones, esters of benzoic acid or salicylic acid,acrylates, alkoxycinnamates, oxamides, oxanilides, benzoxazinones, orbenzoxazoles.

In a preferable embodiment, examples of the radical scavenger group orthe ultraviolet ray absorbing group include:

In this embodiment, X¹ may be each independently a 3-10 valent organicgroup.

In the formula, t is each independently an integer of 1-10. In apreferable embodiment, t is an integer of 1-6. In another preferableembodiment, t is an integer of 2-10, preferably an integer of 2-6.

In the formula, X² is each independently at each occurrence a singlebond or a divalent organic group. X² is preferably an alkylene grouphaving 1-20 carbon atoms, more preferably —(CH₂)_(u)— wherein u is aninteger of 0-2.

The preferable compound of the formulae (A1) and (A2) is a compound ofthe formula (A1′) and (A2′):

PFPE is each independently a group of the formula:

—(OC₄F₈)_(a)—(OC₃F₆)_(b)—(OC₂F₄)_(c)—(OCF₂)_(d)—

wherein a, b, c and d are each independently an integer of 0-200, thesum of a, b, c and d is one or more, and the occurrence order of therespective repeating units in parentheses with the subscript a, b, c ord is not limited in the formula,

Rf is each independently at each occurrence an alkyl group having 1-16carbon atoms which may be substituted by one or more fluorine atoms;

R¹ is each independently at each occurrence a hydroxyl group or ahydrolyzable group;

R² is each independently at each occurrence a hydrogen atom or an alkylgroup having 1-22 carbon atoms;

R¹¹ is each independently at each occurrence a hydrogen atom or ahalogen atom;

R¹² is each independently at each occurrence a hydrogen atom or a loweralkyl group;

n1 is an integer of 1-3, preferably 3;

X¹ is —O—CFR¹³—(CF₂)_(e)—;

R¹³ is a fluorine atom or a lower fluoroalkyl group;

e is 0 or 1;

X² is —(CH₂)_(u)—;

u is an integer of 0-2 (when u is 0, X² is a single bond); and

t is an integer of 1-10.

The compound of the formulae (A1) and (A2) can be obtained for exampleby introducing an iodine into in the end of a perfluoropolyetherderivative corresponding to the Rf-PFPE moiety as a raw material, andthen reacting it with a vinyl monomer corresponding to —CH₂CR¹²(X²—SiR_(n1)R² _(3−n1))—.

Formulae (B1) and (B2):

(Rf-PFPE)_(β′)-X⁵—(SiR¹ _(n1)R² _(3−n1))_(β)  (B1)

(R² _(3−n1)R¹ _(n1)Si)_(β)—X⁵-PFPE-X⁵—(SiR¹ _(n1)R² _(3−n1))_(β)  (B2)

In the formulae (B1) and (B2), Rf, PFPE, R¹, R² and n1 are as definedabove for the formulae (A1) and (A2).

In the formula, X⁵ is each independently a single bond or a 2-10 valentorganic group. X⁵ is recognized to be a linker which connects between aperfluoropolyether moiety (i.e., an Rf-PFPE moiety or -PFPE- moiety)providing mainly water-repellency, surface slip property and the likeand a silane moiety (specifically, —SiR_(n1)R² _(3−n1)) providing anability to bind to a base material in the compound of the formulae (B1)and (B2). Therefore, X⁵ may be any organic group as long as the compoundof the formula (B1) and (B2) can stably exist.

In the formula, R is an integer of 1-9, and 3′ is an integer of 1-9. βand β′ may be determined depending on the valence number of X⁵, and inthe formula (B1), the sum of β and β ′ is the valence number of X⁵. Forexample, when X⁵ is a 10 valent organic group, the sum of β and R¹ is10, for example, β is 9 and β′ is 1, β is 5 and β′ is 5, or R is 1 andβ′ 9. When X⁵ is a divalent organic group, β and β′ are 1. In theformula (B2), β is a value obtained by subtracting 1 from the valencenumber of X⁵.

X⁵ is preferably a 2-7 valent, more preferably a 2-4 valent, furtherpreferably a divalent organic group.

In one embodiment, X5 is a 2-4 valent organic group, 3 is 1-3, and β′ is1.

In another embodiment, X⁵ is a divalent organic group, β is 1, and β′is 1. In this case, the formulae (B1) and (B2) are represented by thefollowing formulae (B1′) and (B2′).

Rf-PFPE-X⁵—SiR¹ _(n1)R² _(3−n1)  (B1′)

R² _(3−n1)R¹ _(n1)Si—X⁵-PFPE-X⁵—SiR¹ _(n1)R² _(3−n1)  (B2′)

Examples of X⁵ include, but are not particularly limited to, forexample, the same group as those described for X¹.

Among them, a preferable specific embodiment of X⁵ includes:

—CH₂O(CH₂)₂—,—CH₂O(CH₂)₃—,—CH₂O(CH₂)₆—,—CH₂O(CH₂)₃Si(CH₃)₂OSi(CH₃)₂(CH₂)₂—,—CH₂O(CH₂)₃Si(CH₃)₂OSi(CH₃)₂OSi(CH₃)₂(CH₂)₂—,—CH₂O(CH₂)₃Si(CH₃)₂O(Si(CH₃)₂O)₂Si(CH₃)₂(CH₂)₂—,—CH₂O(CH₂)₃Si(CH₃)₂O(Si(CH₃)₂O)₃Si(CH₃)₂(CH₂)₂—,—CH₂O(CH₂)₃Si(CH₃)₂O(Si(CH₃)₂O)₁₀Si(CH₃)₂(CH₂)₂—,—CH₂O(CH₂)₃Si(CH₃)₂O(Si(CH₃)₂O)₂₀Si(CH₃)₂(CH₂)₂—,—CH₂OCF₂CHFOCF₂—,—CH₂OCF₂CHFOCF₂CF₂CF₂—,—CH₂OCHCF₂CF₂OCF₂—,—CH₂OCH₂CF₂CF₂OCF₂CF₂—,—CH₂OCH₂CF₂CF₂OCF₂CF₂CF₂—,—CH₂OCH₂CF₂CF₂OCF(CF₃)CF₂OCF₂—,—CH₂OCH₂CF₂CF₂OCF(CF₃)CF₂OCF₂CF₂—,—CH₂OCH₂CF₂CF_OCF(CF₃)CF₂OCF₂CF₂CF₂—,—CH₂OCH₂CHFCF₂OCF₂—,—CH₂OCH₂CHFCF₂OC₂CF₂—,—CH₂OCH₂CHFCF₂OCF₂CF₂—,—CH₂OCH₂CHFCF₂OCF(CF₃)CF₂OCF₂—,—CH₂OCH₂CHFCF₂OCF(CF₃)CF₂OCF₂CF₂—,—CH₂OCH₂CHFCF₂OCF(CF₃)CF₂OCF₂CF₂CF₂——CH₂OCH₂(CH₂)₇CH₂Si(OCH₃)₂OSi(OCH₃)₂(CH₂)₂Si(OCH₃)₂OSi(OCH₃)₂(CH₂)₂—,—CH₂OCH₂CH₂CH₂Si(OCH₃)₂OSi(OCH₃)₂(CH₂)₃—,—CH₂OCH₂CH₂CH₂Si(OCH₂CH₃)₂OSi(OCH₂CH₃)₂(CH₂)₃——CH₂OCH₂CH₂CH₂Si(OCH₃)₂OSi(OCH₃)₂(CH₂)₃—,—CH₂OCH₂CH₂CH₂Si(OCH₂CH₃)₂OSi(OCH₂CH₃)₂(CH₂)₂—,—(CH₂)₂—,—(CH₂)₃—,—(CH₂)₄—,—(CH₂)₅—,—(CH₂)₆—,—(CH₂)₂—Si(CH₃)₂—(CH₂)₂—

—CONH—(CH₂)—,

—CONH—(CH₂)₂—,—CONH—(CH₂)₃—,—CON(CH₃)—(CH₂)₃—,—CON(Ph)-(CH₂)₃— wherein Ph is phenyl,—CONH—(CH₂)₆—,—CON(CH₃)—(CH₂)₆—,—CON(Ph)-(CH₂)₆— wherein Ph is phenyl,—CONH—(CH₂)₂NH(CH₂)₃—,—CONH—(CH₂)₆NH(CH₂)₃—,—CH₂O—CONH—(CH₂)₃—,—CH₂O—CONH—(CH₂)₆—,—S—(CH₂)₃—,—(CH₂)₂S(CH₂)₃—,—CONH—(CH₂)₃Si(CH₃)₂OSi(CH₃)₂(CH₂)₂—,—CONH—(CH₂)₃Si(CH₃)₂OSi(CH₃)₂OSi(CH₃)₂(CH₂)₂——CONH—(CH₂)₃Si(CH₃)₂O(Si(CH₃)₂O)₂Si(CH₃)₂(CH₂)₂—,—CONH—(CH₂)₃Si(CH₃)₂O(Si(CH₃)₂O)₃Si(CH₃)₂(CH₂)₂—,—CONH—(CH₂)₃Si(CH₃)₂O(Si(CH₃)₂O)₁₀Si(CH₃)₂(CH₂)₂—,—CONH—(CH₂)₃Si(CH₃)₂O(Si(CH₃)₂O)₂₀Si(CH₃)₂(CH₂)₂——C(O)O—(CH₂)₃—,—C(O)O—(CH₂)₆—,—CH₂—O—(CH₂)₃—Si(CH₃)₂—(CH₂)₂—Si(CH₃)₂—(CH₂)₂—,—CH₂—O—(CH₂)₃—Si(CH₃)₂—(CH₂)₂—Si(CH₃)₂—CH(CH₃)—,—CH₂—O—(CH₂)₃—Si(CH₃)₂—(CH₂)₂—Si(CH₃)₂—(CH₂)₃——CH₂—O—(CH₂)₃—Si(CH₃)₂—(CH₂)₂—Si(CH₃)₂—CH(CH₃)—CH₂—,

—OCH₂—,

—O(CH₂)₃—

—OCFHCF₂—,

The preferable compound of the formulae (B1) and (B2) is a compound ofthe formula (B1′) and (B2′):

Rf-PFPE-X⁵—SiR¹ _(n1)R² _(3−n1)  (B1′)

R² _(3−n1)R¹ _(n1)Si—X⁵-PFPE-X⁵—SiR¹ _(n1)R² _(3−n1)  (B2′)

wherein:

PFPE is each independently a group of the formula:

—(OC₄F₈)_(a)—(OC₃F₆)_(b)—(OC₂F₄)_(c)—(OCF₂)_(d)—

wherein a, b, c and d are each independently an integer of 0-200, thesum of a, b, c and d is one or more, and the occurrence order of therespective repeating units in parentheses with the subscript a, b, c ord is not limited in the formula,

Rf is each independently at each occurrence an alkyl group having 1-16carbon atoms which may be substituted by one or more fluorine atoms;

R¹ is each independently at each occurrence a hydroxyl group or ahydrolyzable group;

R² is each independently at each occurrence a hydrogen atom or an alkylgroup having 1-22 carbon atoms; n1 is an integer of 0-2, preferably 0;and

X⁵ is —CH₂O(CH₂)₂—, —CH₂O(CH₂)₃— or —CH₂O(CH₂)₆—.

The compound of the formulae (B1) and (B2) can be prepared by a knownmethod, for example, a method described in Patent Document 1 or themodified method thereof. For example, the compound of the formulae (B1)and (B2) can be prepared by reacting a compound of the formula (B1-4) or(B2-4):

(Rf-PFPE)_(β′)-X^(5′)—(R⁹²—CH═CH₂)_(β)  (B1-4)

(CH₂═CH—R⁹²)_(β)—X^(5′)-PFPE-X^(5′)—(R⁹²—CH═CH₂)_(β)  (B2-4)

wherein:

PFPE is each independently a group of the formula:

—(OC₄F₈)_(a)—(OC₃F₆)_(b)—(OC₂F₄)_(c)—(OCF₂)_(d)—

wherein a, b, c and d are each independently an integer of 0-200, thesum of a, b, c and d is one or more, and the occurrence order of therespective repeating units in parentheses with the subscript a, b, c ord is not limited in the formula,

Rf is each independently at each occurrence an alkyl group having 1-16carbon atoms which may be substituted by one or more fluorine atoms;

X⁵, is each independently a single bond or a 2-10 valent organic group;

β is each independently an integer of 1-9;

β′ is each independently an integer of 1-9; and

R⁹² is a single bond or a divalent organic group, with HSiM₃ wherein Mis each independently a halogen atom, R¹ or R², R² is each independentlyat each occurrence a hydroxyl group or a hydrolyzable group, R¹ is eachindependently at each occurrence a hydrogen atom or an alkyl grouphaving 1-22 carbon atoms, and as necessary, converting the halogen atomto R¹ or R², as a compound of the formula (B1″) or (B2″):

(Rf-PFPE)_(β′)-X^(5′)—(R⁹²—CH₂CH₂—SiR¹ _(n1)R² _(3−n1))_(β)  (B1″)

(R¹ _(n)R²_(3−n1)Si—CH₂CH₂—R⁹²)_(β)—X^(5′)-PFPE-X^(5′)—**(R⁹²—CH₂CH—SiR¹ _(n1)R²_(3−n1))_(β)  (B2″)

wherein PFPE, Rf, X^(5′), β, β′ and R⁹² are as defined above; and

n1 is an integer of 0-3.

In the formula (B1″) or (B2″), the portion from X⁵ to R⁸²—CH₂CH₂—corresponds to X⁵ in the formula (B1) or (B2). Therefore, the preferableX^(5′) is a group excluding a portion corresponding to —R⁹²—CH₂CH₂— fromthe preferable X⁵ described above.

Formulae (C1) and (C2):

(Rf-PFPE)_(γ′)-X⁷—(SiR^(a) _(k1)R^(b) _(l1)R^(c) _(m1))_(γ)  (C1)

(R^(c) _(m1)R^(b) _(l1)R^(a) _(k1)Si)_(γ)—X⁷-PFPE-X⁷—(SiR^(a) _(k1)R^(b)_(l1)R^(c) _(m1))_(γ)  (C2)

In the formulae (C1) and (C2), Rf and PFPE are as defined for theformulae (A1) and (A2).

In the formula, X⁷ is each independently a single bond or a 2-10 valentorganic group. X⁷ is recognized to be a linker which connects between aperfluoropolyether moiety (an Rf-PFPE moiety or -PFPE- moiety) providingmainly water-repellency, surface slip property and the like and a silanemoiety (specifically, —SiR^(a) _(k1)R^(b) _(l1)R^(c) _(m1)) providing anability to bind to a base material in the compound of the formula (C1)and (C2). Therefore, X⁷ may be any organic group as long as the compoundof the formula (C1) and (C2) can stably exist.

In the formula, γ is an integer of 1-9, and γ′ is an integer of 1-9. γand γ′ may be determined depending on the valence number of X⁷, and inthe formula (C1), the sum of γ and γ′ is the valence number of X⁷. Forexample, when X⁷ is a 10 valent organic group, the sum of γ and γ′ is10, for example, γ is 9 and γ′ is 1, γ is 5 and γ′ is 5, or γ is 1 andγ′ is 9. When X⁷ is a divalent organic group, γ and γ′ are 1. In theformula (C1), γ is a value obtained by subtracting 1 from the valencenumber of X⁷.

X⁷ is preferably a 2-7 valent, more preferably a 2-4 valent, furtherpreferably a divalent organic group.

In one embodiment, X⁷ is a 2-4 valent organic group, γ is 1-3, and γ′ is1.

In another embodiment, X⁷ is a divalent organic group, γ is 1, and γ′is 1. In this case, the formulae (C1) and (C2) are represented by thefollowing formulae (C1′) and (C2′).

Rf-PFPE-X⁷—SiR^(a) _(k1)R^(b) _(l1)R^(c) _(m1)  (C1′)

R^(c) _(m1)R^(b) _(l1)R^(a) _(k1)Si—X⁵-PFPE-X⁷—SiR^(a) _(k1)R^(b)_(l1)R^(c) _(m1)  (C2′)

Examples of X⁷ include, but are not particularly limited to, forexample, the same groups as those described for X¹.

Among them, a preferable specific embodiment of X¹ includes:

—CH₂O(CH₂)₂—,—CH₂O(CH₂)₃—,—CH₂O(CH₂)₆—,—CH₂O(CH₂)₃Si(CH₃)₂OSi(CH₃)₂(CH₂)₂—,—CH₂O(CH₂)₃Si(CH₃)₂OSi(CH₃)₂OSi(CH₃)₂(CH₂)₂—,—CH₂O(CH₂)₃Si(CH₃)₂O(Si(CH₃)₂O)₂Si(CH₃)₂(CH₂)₂—,—CH₂O(CH₂)₃Si(CH₃)₂O(Si(CH₃)₂O)₃Si(CH₃)₂(CH₂)₂—,—CH₂O(CH₂)₃Si(CH₃)₂O(Si(CH₃)₂O)₁₀Si(CH₃)₂(CH₂)₂—,—CH₂O(CH₂)₃Si(CH₃)₂O(Si(CH₃)₂O)₂₀Si(CH₃)₂(CH₂)₂—,—CH₂OCF₂CHFOCF₂—,—CH₂OCF₂CHFOCF₂CF₂—,—CH₂OCF₂CHFOCF₂CF₂CF₂—,—CH₂OCH₂CF₂CF₂OCF₂—,—CH₂OCH₂CF₂CF₂OCF₂CF₂—,—CH₂OCH₂CF₂CF₂OCF₂CF₂CF₂—,—CH₂OCH₂CF₂CF₂OCF(CF₃)CF₂OCF₂—,—CH₂OCH₂CF₂CF₂OCF(CF₃)CF₂OCF₂CF₂—,—CH₂OCH₂CF₂CF₂OCF(CF₃)CF₂OCF₂CF₂CF₂—,—CH₂OCH₂CHFCF₂OCF₂—,—CH₂OCH₂CHFCF₂OCF₂CF₂—,—CH₂OCH₂CHFCF₂OCF₂CF₂CF₂—,—CH₂OCH₂CHFCF₂OCF(CF₃)CF₂OCF₂—,—CH₂OCH₂CHFCF₂OCF(CF₃)CF₂OCF₂CF₂—,—CH₂OCH₂CHFCF₂OCF(CF₃)CF₂OCF₂CF₂CF₂—,—CH₂OCH₂(CH₂)₇CH₂Si(OCH₃)₂OSi(OCH₃)₂(CH₂)₂Si(OCH₃)₂OSi(OCH₃)₂(CH₂)₂—,—CH₂OCH₂CH₂CH₂Si(OCH₃)₂OSi(OCH₃)₂(CH₂)₃—,—CH₂OCH₂CH₂CH₂Si(OCH₂CH₃)₂OSi(OCH₂CH₃)₂(CH₂)₂—,—CH₂OCH₂CH₂CH₂Si(OCH₃)₂OSi(OCH₃)₂(CH₂)₂—,—CH₂OCH₂CH₂CH₂Si(OCH₂CH₃)₂OSi(OCH₂CH₃)₂(CH₂)₂—,—(CH₂)₂—,—(CH₂)₃—,—(CH₂)₄—,—(CH₂)₅—,—(CH₂)₆—,—(CH₂)₂—Si(CH₃)₂—(CH₂)₂—

—CONH—(CH₂)—,

—CONH—(CH₂)₂—,—CONH—(CH₂)₃—,—CON(CH₃)—(CH₂)₃—,—CON(Ph)-(CH₂)₃— wherein Ph is phenyl,—CONH—(CH₂)₆—,—CON(CH₃)—(CH₂)₆—,—CON(Ph)-(CH₂)₆— wherein Ph is phenyl,—CONH—(CH₂)₂NH(CH₂)₃—,—CONH—(CH₂)₆NH(CH₂)₃—,—CH₂O—CONH—(CH₂)₃—,—CH₂O—CONH—(CH₂)₆—,—S—(CH₂)₃—,—(CH₂)₂S(CH₂)₃—,—CONH—(CH₂)₃Si(CH₃)₂OSi(CH₃)₂(CH₂)₂—,—CONH—(CH₂)₃Si(CH₃)₂OSi(CH₃)₂OSi(CH₃)₂(CH₂)₂——CONH—(CH₂)₃Si(CH₃)₂O(Si(CH₃)₂O)₂Si(CH₃)₂(CH₂)₂—,—CONH—(CH₂)₃Si(CH₃)₂O(Si(CH₃)₂O)₃Si(CH₃)₂(CH₂)₂—,—CONH—(CH₂)₃Si(CH₃)₂O(Si(CH₃)₂O)₁₀Si(CH₃)₂(CH₂)₂—,—CONH—(CH₂)₃Si(CH₃)₂O(Si(CH₃)₂O)₂₀Si(CH₃)₂(CH₂)₂——C(O)O—(CH₂)₃—,—C(O)O—(CH₂)₆—,—CH₂—O—(CH₂)₃—Si(CH₃)₂—(CH₂)₂—Si(CH₃)₂—(CH₂)₂—,—CH₂—O—(CH₂)₃—Si(CH₃)₂—(CH₂)₂—Si(CH₃)₂—CH(CH₃)—,—CH₂—O—(CH₂)₃—Si(CH₃)₂—(CH₂)₂—Si(CH₃)₂—(CH₂)₃——CH₂—O—(CH₂)₃—Si(CH₃)₂—(CH₂)₂—Si(CH₃)₂—CH(CH₃)—CH₂—,

—OCH₂—,

—O(CH₂)₃—

—OCFHCF₂—,

In the formula, R^(a) is each independently at each occurrence —Z¹—SiR⁷¹_(p1)R⁷² _(q1)R⁷³ _(r1).

In the formula, Z¹ is each independently at each occurrence an oxygenatom or a divalent organic group.

Z¹ is preferably a divalent organic group, and does not include a groupwhich forms a siloxane bond together with a Si atom (the Si atom bindingto R^(a)) present in the end of the molecular backbone of the formula(C1) or the formula (C2).

Z¹ is preferably a C₁₋₆ alkylene group, —(CH₂)_(q)—O—(CH₂)_(h)— (whereing is an integer of 1-6, h is an integer of 1-6) or -phenylene-(CH₂)_(i)—(wherein i is an integer of 0-6), more preferably a C₁₋₃ alkylene group.These groups may be substituted with, for example, one or moresubstituents selected form a fluorine atom, a C₁₋₆ alkyl group, a C₂₋₆alkenyl group, and a C₂₋₆ alkynyl group.

In the formula, R⁷¹ is each independently at each occurrence R^(a′).R^(a′) is as defined for R^(a).

In R^(a), the number of Si atoms which are linearly connected via Z¹ isup to five. That is, in R^(a), when there is at least one R⁷¹, there aretwo or more Si atoms which are linearly connected via Z¹ in R^(a). Thenumber of such Si atoms which are linearly connected via Z is five atmost. It is noted that “the number of such Si atoms which are linearlyconnected via Z in R^(a) is equal to the repeating number of —Z¹—Si—which are linearly connected in R^(a).

For example, one example in which Si atoms are connected via Z¹ (it isshown as Z simply below) in R^(a) is shown below.

In the above formula, * represents a position binding to Si of the mainbackbone, and . . . represents that a predetermined group other than ZSibinds thereto, that is, when all three bonds of a Si atom are . . . , itmeans an end point of the repeat of ZSi. The number on the rightshoulder of Si means the number of occurrences of Si which is linearlyconnected via the Z group from *. In other words, in the chain in whichthe repeat of ZSi is completed at Si², “the number of such Si atomswhich are linearly connected via the Z group in R^(a)” is 2. Similarly,in the chain in which the repeat of ZSi is completed at Si³, Si⁴ andSi⁵, respectively, “the number of such Si atoms which are linearlyconnected via the Z¹ group in R^(a)” is 3, 4 and 5. It is noted that asseen from the above formula, there are some ZSi chains, but they neednot have the same length and may be have arbitrary length.

In a preferred embodiment, as shown below, “the number of such Si atomswhich are linearly connected via the Z group in R^(a)” is 1 (leftformula) or 2 (right formula) in all chains.

In one embodiment, the number of such Si atoms which are linearlyconnected via the Z group in R^(a) is 1 or 2, preferably 1.

In the formula, R⁷² is each independently at each occurrence a hydroxylgroup or a hydrolyzable group.

The “hydrolyzable group” as used herein represents a group which is ableto undergo a hydrolysis reaction. Examples of the hydrolyzable groupinclude —OR, —OCOR, —O—N═C(R)₂, —N(R)₂, —NHR, halogen (wherein R is asubstituted or non-substituted alkyl group having 1-4 carbon atoms),preferably —OR (an alkoxy group). Examples of R include anon-substituted alkyl group such as a methyl group, an ethyl group, apropyl group, an isopropyl group, a n-butyl group, an isobutyl group; asubstituted alkyl group such as a chloromethyl group. Among them, analkyl group, in particular a non-substituted alkyl group is preferable,a methyl group or an ethyl group is more preferable. The hydroxyl groupmay be, but is not particularly limited to, a group generated byhydrolysis of a hydrolyzable group.

Preferably, R⁷² is —OR wherein R is a substituted or unsubstituted C₁₋₃alkyl group, more preferably a methyl group.

In the formula, R⁷³ is each independently at each occurrence a hydrogenatom or a lower alkyl group. The lower alkyl group is preferably analkyl group having 1-20 carbon atoms, more preferably an alkyl grouphaving 1-6 carbon atoms, further preferably a methyl group.

In the formula, p1 is each independently at each occurrence an integerof 0-3; q1 is each independently at each occurrence an integer of 0-3;and r1 is each independently at each occurrence an integer of 0-3. Thesum of p1, q1 and r1 is 3.

In a preferable embodiment, in R^(a′) at the end of R^(a) (R^(a) whenR^(a′) is absent), q1 is preferably 2 or more, for example, 2 or 3, morepreferably 3.

In a preferable embodiment, at least one of the end portions in R^(a)may be —Si(—Z¹—SiR⁷² _(q)R⁷³ _(r))₂ or —Si(—Z¹—SiR⁷² _(q)R⁷³ _(r))₃,preferably —Si(—Z¹—SiR⁷² _(q)R⁷³ _(r))₂. In the formula, the unit(—Z¹—SiR⁷² _(q)R⁷³ _(r)) is preferably (—Z¹—SiR⁷² ₃). In a furtherpreferable embodiment, all end portions in R^(a) may be —Si(—Z¹—SiR⁷²_(q)R⁷³ _(r))₃, preferably —Si(—Z¹—SiR⁷² ₃)₃.

In the formulae (C1) and (C2), at least one R⁷² is present.

In the formula, R^(b) is each independently at each occurrence ahydroxyl group or a hydrolyzable group.

R^(b) is preferably a hydroxyl group, —OR, —OCOR, —O—N═C(R)₂, —N(R)₂,—NHR, halogen (wherein R is a substituted or unsubstituted alkyl grouphaving 1-4 carbon atoms), more preferably —OR. R is an unsubstitutedalkyl group such as a methyl group, an ethyl group, a propyl group, anisopropyl group, a n-butyl group, an isobutyl group; a substituted alkylgroup such as a chloromethyl group. Among them, an alkyl group, inparticular unsubstituted alkyl group is preferable, and a methyl groupor an ethyl group is more preferable. The hydroxyl group may be, but isnot particularly limited to, a group generated by hydrolysis of ahydrolyzable group. More preferably, R^(c) is —OR wherein R is asubstituted or unsubstituted C₁₋₃ alkyl group, more preferably a methylgroup.

In the formula, R^(c) is each independently at each occurrence ahydrogen atom or a lower alkyl group. The lower alkyl group ispreferably an alkyl group having 1-20 carbon atoms, more preferably analkyl group having 1-6 carbon atoms, further preferably a methyl group.

In the formula, k1 is each independently at each occurrence an integerof 0-3; 11 is each independently at each occurrence an integer of 0-3;m1 is each independently at each occurrence an integer of 0-3. The sumof k1, l1 and m1 is 3.

The compound of the formulae (C1) and (C2) can be prepared, for example,by introducing a hydroxyl group in the end of a perfluoropolyetherderivative corresponding to the Rf-PFPE moiety as a raw material,followed by further introducing a group having an unsaturated group inthe end thereof, and reacting the group having an unsaturated group witha silyl derivative having a halogen atom, further introducing a hydroxylgroup in the end of the silyl group, and then reacting the group havingan unsaturated group with a silyl derivative. For example, the compoundcan be prepared as follows.

The preferable compound of the formulae (C1) and (C2) a compound of thefollowing formulae (C1″) and (C2″):

Rf-PFPE-X⁷—SiR^(a) ₃  (C1″)

R^(a) ₃Si—X⁷-PFPE-X⁷—SiR^(a) ₃  (C2″)

wherein:

PFPE is each independently a group of the formula:

—(OC₄F₈)_(a)—(OC₃F₆)_(b)—(OC₂F₄)_(c)—(OCF₂)_(d)—

wherein a, b, c and d are each independently an integer of 0-200, thesum of a, b, c and d is 1 or more, and the occurrence order of therespective repeating units in parentheses with the subscript a, b, c ord is not limited in the formula;

Rf is each independently at each occurrence an alkyl group having 1-16carbon atoms which may be substituted by one or more fluorine atoms;

X⁷ is —CH₂O(CH₂)₂—, —CH₂O(CH₂)₃— or —CH₂O(CH₂)₆—;

R^(a) is each independently at each occurrence —Z¹—SiR⁷¹ _(p1)R⁷²_(q1)R⁷³ _(r1);

Z¹ is a C₁₋₆ alkylene group;

R⁷² is each independently at each occurrence R^(a);

R^(a′) has the same definition as that of R^(a);

in R^(a), the number of Si atoms which are straightly linked via the Z¹group is up to five;

R⁷² is each independently at each occurrence a hydroxyl group or ahydrolyzable group;

R⁷³ is each independently at each occurrence a hydrogen atom or a loweralkyl group;

p1 is each independently at each occurrence an integer of 0-2;

q1 is each independently at each occurrence an integer of 1-3,preferably 3;

r1 is each independently at each occurrence an integer of 0-2; and

in one R^(a), the sum of p1, q1 and r1 is 3.

In the compound of the formulae (C1) and (C2), for example, thefollowing formulae (C1-4) or (C2-4):

(Rf-PFPE)_(γ′)-X^(7′)—(R⁹²—CH═CH₂)_(γ)  (C1-4)

(CH₂═CH—R⁹²)_(γ)—X^(7′)-PFPE-X^(7′)—(R⁹²—CH═CH₂)_(γ)  (C2-4)

wherein:

PFPE is each independently a group of the formula:

—(OC₄F₈)_(a)—(OC₃F₆)_(b)—(OC₂F₄)_(c)—(OCF₂)_(d)—

-   -   wherein a, b, c and d are each independently an integer of        0-200, the sum of a, b, c and d is 1 or more, and the occurrence        order of the respective repeating units in parentheses with the        subscript a, b, c or d is not limited in the formula;

Rf is each independently at each occurrence an alkyl group having 1-16carbon atoms which may be substituted by one or more fluorine atoms;

X^(7′) is each independently a single bond or a 2-10 valent organicgroup;

γ is each independently an integer of 1-9;

γ′ is each independently an integer of 1-9; and

R⁹² is a single bond or a divalent organic group, is reacted with acompound of HSiR⁹³ _(k1)R^(b) _(l1)R^(c) _(m1) wherein R⁹³ is a halogenatom, for example a fluorine atom, a chlorine atom, a bromine atom or aniodine atom, preferably a chlorine atom, R^(b) is each independently ateach occurrence a hydroxyl group or a hydrolyzable group, R^(c) is eachindependently at each occurrence a hydrogen atom or a lower alkyl group,k1 is an integer of 1-3, l1 and m1 are each independently an integer of0-2, and the sum of k1, l1 and m1 is 3,

to obtain a compound of the formula (C1-5) or (C2-5):

(Rf-PFPE)_(γ′)-X^(7′)—(R⁹²—CH₂CH₂—SiR⁹³ _(k1)R^(b) _(l1)R^(c)_(m1))_(γ)  (C1-5)

(R^(c) _(m1)R^(b) _(l1)R⁹³_(k1)—Si—CH₂CH₂—R⁹²)_(γ)—X^(7′)-PFPE-*X^(7′)—(R⁹²—CH₂CH—SiR⁹³ _(k1)R^(b)_(l1)R^(c) _(m1))_(γ)  (C2-5)

wherein Rf, PFPE, R⁹², R⁹⁴, R^(b), R^(c), γ, γ′, X^(7′), k1, l1 and m1are as defined above.

The compound of the formula (C1-5) or (C2-5) obtained is reacted with acompound of Hal-J-R⁹⁴—CH═CH₂ wherein Hal is a halogen atom (for example,I, Br, Cl, F, or the like), J is Mg, Cu, Pd or Zn, and R⁹⁴ is a singlebond or a divalent organic group, to obtain a compound of the formula(C1-6) or (C2-6):

(Rf-PFPE)_(γ′)-X^(7′)—(R⁹²—CH₂CH₂—SiR^(b) _(l1)R^(c)_(m1)(R⁹⁴—CH═CH)_(k1))  (C1-6)

((CH═CH₂—R⁹⁴)_(k1)R^(c) _(m1)R^(b)_(l1)Si—CH₂CH—R⁹²)_(γ)—X^(7′)-PFPE-**X^(7′)—(R⁹²—CH₂CH₂—SiR^(b)_(l1)R^(c) _(m1)(R⁹⁴—CH═CH₂)_(k1))_(γ)  (C2-6)

wherein Rf, PFPE, R⁹², R⁹⁴, R^(b), R^(c), γ, γ′, X^(7′), k1, l1 and m1are as defined above.

The compound of the formula (C1-6) or (C2-6) obtained can be reactedwith HSiM₃ (wherein M is each independently a halogen atom, R⁷² or R⁷³,R⁷² is each independently at each occurrence a hydroxyl group or ahydrolyzable group, and R⁷³ is each independently at each occurrence ahydrogen atom or a lower alkyl group), and as necessary, converting thehalogen atom the halogen atom to R⁷² or R⁷³ to obtain a compound of theformula (C1′″) or (C2′″):

(Rf-PFPE)_(γ′)—X^(7′)—(R⁹²—CH₂CH₂—SiR^(b) _(l1)R^(c)_(m1)(R⁹⁴—CH₂CH₂—SiR⁷² _(q1)R⁷³ _(r1))_(k1))γ  (C1′″)

((R⁷² _(q1)R⁷³ _(r1)Si—CH₂CH₂—R⁹⁴)_(k1)R^(c) _(m1)R^(b)_(l1)Si—CH₂CH₂—R⁹²)—X^(7′)-PFPE-**X^(7′)—(R⁹²—CH₂CH₂—SiR^(b) _(l1)R^(c)_(m1)(R⁹⁴—CH₂CH₂—SiR⁷² _(q1)R⁷³ _(r1))_(k1))γ  (C2′″)

wherein

Rf, PFPE, R¹², R⁷³, R⁹², R⁹⁴, R^(b), R, γ, γ′, X^(7′), k1, l1 and m1 areas defined above;

q1 is each independently at each occurrence an integer of 1-3; and

r1 is each independently at each occurrence an integer of 0-2.

In the formula (C1′″) or (C2′″), a portion from X^(7′) to R⁹²—CH₂CH₂—corresponds to X⁷ in the formula (C1) or (C2), and —R⁹⁴—CH₂CH₂—corresponds to Z in the formula (C1) or (C2).

Formulae (D1) and (D2):

(Rf-PFPE)_(δ′)-X⁹—(CR^(d) _(k2)R^(e) _(l2)R^(f) _(m2))_(δ)  (D1)

(R^(f) _(m2)R^(e) _(l2)R^(d) _(k2)C)_(δ)—X⁹-PFPE-X—(CR^(d) _(k2)R^(e)_(l2)R^(f) _(m2))_(δ)  (B2)

In the formulae (D1) and (D2), Rf and PFPE are as defined for theformulae (A1) and (A2).

In the formula, X⁹ is each independently a single bond or a 2-10 valentorganic group. X⁹ is recognized to be a linker which connects between aperfluoropolyether moiety (i.e., an Rf-PFPE moiety or -PFPE- moiety)providing mainly water-repellency, surface slip property and the likeand a moiety (i.e., a group in parentheses with the subscript 6)providing an ability to bind to a base material in the compound of theformula (D1) and (D2). Therefore, X⁹ may be any organic group as long asthe compound of the formula (D1) and (D2) can stably exist.

In the formula, δ is an integer of 1-9, and δ′ is an integer of 1-9. δand δ′ may be determined depending on the valence number of X, and inthe formula (D1), the sum of δ and δ′ is the valence number of X. Forexample, when X is a 10 valent organic group, the sum of δ and δ′ is 10,for example, δ is 9 and δ′ is 1, δ is 5 and δ′ is 5, or δ is 1 and δ′ is9. When X⁹ is a divalent organic group, δ and 5′ are 1. In the formula(D1), δ is a value obtained by subtracting 1 from the valence number ofX⁹.

X⁹ is preferably a 2-7 valent, more preferably a 2-4 valent, furtherpreferably a divalent organic group.

In one embodiment, X⁹ is a 2-4 valent organic group, γ is 1-3, and γ′ is1.

In another embodiment, X⁹ is a divalent organic group, γ is 1, and γ′is 1. In this case, the formulae (D1) and (D2) are represented by thefollowing formulae (D1′) and (D2′).

Rf-PFPE-X⁹—CR^(d) _(k2)R^(e) _(l2)R^(f) _(m2)  (D1)

R^(f) _(m2)R^(e) _(l2)R^(d) _(k2)C—X⁹-PFPE-X⁹—CR^(d) _(k2)R^(e)_(l2)R^(f) _(m2)  (B2)

Examples of X⁹ include, but are not particularly limited to, forexample, the same groups as those described for X¹.

Among them, a preferable specific embodiment of X includes:

—CH₂O(CH₂)₂—,—CH₂O(CH₂)₃—,—CH₂O(CH₂)₆—,—CH₂O(CH₂)₃Si(CH₃)₂OSi(CH₃)₂(CH₂)₂—,—CH₂O(CH₂)₃Si(CH₃)₂OSi(CH₃)₂OSi(CH₃)₂(CH₂)₂—,—CH₂O(CH₂)₃Si(CH₃)₂O(Si(CH₃)₂O)₂Si(CH₃)₂(CH₂)₂—,—CH₂O(CH₂)₃Si(CH₃)₂O(Si(CH₃)₂O)₃Si(CH₃)₂(CH₂)₂—,—CH₂O(CH₂)₃Si(CH₃)₂O(Si(CH₃)₂O)₁₀Si(CH₃)₂(CH₂)₂—,—CH₂O(CH₂)₃Si(CH₃)₂O(Si(CH₃)₂O)₂₀Si(CH₃)₂(CH₂)₂—,—CH₂OCF₂CHFOCF₂—,—CH₂OCF₂CHFOCF₂CF₂—,—CH₂OCF₂CHFOCF₂CF₂CF₂—,—CH₂OCH₂CF₂CF₂OCF₂—,—CH₂OCH₂CF₂CF₂OCF₂CF₂—,—CH₂OCH₂CF₂CF₂OCF₂CF₂CF₂—,—CH₂OCH₂CF₂CF₂OCF(CF₃)CF₂OCF₂—,—CH₂OCH₂CF₂CF₂OCF(CF₃)CF₂OCF₂CF₂—,—CH₂OCH₂CF₂CF₂OCF(CF₃)CF₂OCF₂CF₂CF₂—,—CH₂OCH₂CHFCF₂OCF₂—,—CH₂OCH₂CHFCF₂OCF₂CF₂—,—CH₂OCH₂CHFCF₂OCF₂CF₂CF₂—,—CH₂OCH₂CHFCF₂OCF(CF₃)CF₂OCF₂—,—CH₂OCH₂CHFCF₂OCF(CF₃)CF₂OCF₂CF₂—,—CH₂OCH₂CHFCF₂OCF(CF₃)CF₂OCF₂CF₂CF₂—,—CH₂OCH₂(CH₂)₇CH₂Si(OCH₃)₂OSi(OCH₃)₂(CH₂)₂Si(OCH₃)₂OSi(OCH₃)₂(CH₂)₂—,—CH₂OCH₂CH₂CH₂Si(OCH₃)₂OSi(OCH₃)₂(CH₂)₃—,—CH₂OCH₂CH₂CH₂Si(OCH₂CH₃)₂OSi(OCH₂CH₃)₂(CH₂)₃——CH₂OCH₂CH₂CH₂Si(OCH₃)₂OSi(OCH₃)₂(CH₂)₃—,—CH₂OCH₂CH₂CH₂Si(OCH₂CH₃)₂OSi(OCH₂CH₃)₂(CH₂)₂—,—(CH₂)₂—,—(CH₂)₃—,—(CH₂)₄—,—(CH₂)₅—,—(CH₂)₆—,—(CH₂)₂—Si(CH₃)₂—(CH₂)₂—

—CONH—(CH₂)—,

—CONH—(CH₂)₂—,—CONH—(CH₂)₃—,—CON(CH₃)—(CH₂)₃—,—CON(Ph)-(CH₂)₃— wherein Ph is phenyl,—CONH—(CH₂)₆—,—CON(CH₃)—(CH₂)₆—,—CON(Ph)-(CH₂)₆— wherein Ph is phenyl,—CONH—(CH₂)₂NH(CH₂)₃—,—CONH—(CH₂)₆NH(CH₂)₃—,—CH₂O—CONH—(CH₂)₃—,—CH₂O—CONH—(CH₂)₆—,—S—(CH₂)₃—,—(CH₂)₂S(CH₂)₃—,—CONH—(CH₂)₃Si(CH₃)₂OSi(CH₃)₂(CH₂)₂—,—CONH—(CH₂)₃Si(CH₃)₂OSi(CH₃)₂OSi(CH₃)₂(CH₂)₂——CONH—(CH₂)₃Si(CH₃)₂O(Si(CH₃)₂O)₂Si(CH₃)₂(CH₂)₂—,—CONH—(CH₂)₃Si(CH₃)₂O(Si(CH₃)₂O)₃Si(CH₃)₂(CH₂)₂—,—CONH—(CH₂)₃Si(CH₃)₂O(Si(CH₃)₂O)₁₀Si(CH₃)₂(CH₂)₂—,—CONH—(CH₂)₃Si(CH₃)₂O(Si(CH₃)₂O)₂₀Si(CH₃)₂(CH₂)₂——C(O)O—(CH₂)₃—,—C(O)O—(CH₂)₆—,—CH₂—O—(CH₂)₃—Si(CH₃)₂—(CH₂)₂—Si(CH₃)₂—(CH₂)₂—,—CH₂—O—(CH₂)₃—Si(CH₃)₂—(CH₂)₂—Si(CH₃)₂—CH(CH₃)—,—CH₂—O—(CH₂)₃—Si(CH₃)₂—(CH₂)₂—Si(CH₃)₂—(CH₂)₃——CH₂—O—(CH₂)₃—Si(CH₃)₂—(CH₂)₂—Si(CH₃)₂—CH(CH₃)—CH₂—,

—OCH₂—,

—O(CH₂)₃—

—OCFHCF₂—,

In the formula, R^(d) is each independently at each occurrence —Z²—CR⁸¹_(p2)R⁸² _(q2)R⁸³ _(r2).

In the formula, Z² is each independently at each occurrence, an oxygenatom or a divalent organic group.

Z² is preferably a C₁₋₆ alkylene group, —(CH₂)_(q)—O—(CH₂)_(h)— (whereing is an integer of 0-6, for example, an integer of 1-6, h is an integerof 0-6, for example, an integer of 1-6) or -phenylene-(CH₂)_(i)—(wherein i is an integer of 0-6), more preferably a C₁₋₃ alkylene group.These groups may be substituted with, for example, one or moresubstituents selected form a fluorine atom, a C₁₋₆ alkyl group, a C₂₋₆alkenyl group, and a C₂₋₆ alkynyl group.

In the formula, R⁸¹ is each independently at each occurrence R^(d′).R^(d′) is as defined for R^(d).

In R^(d), the number of C atoms which are linearly connected via Z² isup to five. That is, in R^(d), when there is at least one R⁸¹, there aretwo or more C atoms which are linearly connected via Z² in R^(d). Thenumber of such C atoms which are linearly connected via Z is five atmost. It is noted that “the number of such C atoms which are linearlyconnected via Z² in R^(d) is equal to the repeating number of —Z²—C—which are linearly connected in R^(d).

In a preferred embodiment, as shown below, “the number of such C atomswhich are linearly connected via the Z² group in R^(d) is 1 (leftformula) or 2 (right formula) in all chains.

In one embodiment, the number of such C atoms which are linearlyconnected via the Z² group in R^(d) is 1 or 2, preferably 1.

In the formula, R⁸² is —Y—SiR⁸⁵ _(n2)R⁸⁶ _(3−n2).

Y is each independently at each occurrence a divalent organic group.

In a preferable embodiment, Y is a C₁₋₆ alkylene group,—(CH₂)_(g′)—O—(CH₂)_(h′)— (wherein g′ is an integer of 0-6, for example,an integer of 1-6, and h′ is an integer of 0-6, for example, an integerof 1-6), or -phenylene-(CH₂)_(i′)— (wherein i′ is an integer of 0-6).These groups may be substituted with, for example, one or moresubstituents selected form a fluorine atom, a C₁₋₆ alkyl group, a C₂₋₆alkenyl group, and a C₂₋₆ alkynyl group.

In one embodiment, Y may be a C1-6 alkylene group or —O—(CH₂)_(h′)— or-phenylene-(CH)_(i′)—. When Y is the above group, a light resistance, inparticular an ultraviolet resistance, may be increased.

R⁵ is each independently at each occurrence a hydroxyl group or ahydrolyzable group.

The “hydrolyzable group” as used herein represents a group which is ableto undergo a hydrolysis reaction. Examples of the hydrolyzable groupinclude —OR, —OCOR, —O—N═C(R)₂, —N(R)₂, —NHR, halogen (wherein R is asubstituted or non-substituted alkyl group having 1-4 carbon atoms),preferably —OR (an alkoxy group). Examples of R include anon-substituted alkyl group such as a methyl group, an ethyl group, apropyl group, an isopropyl group, a n-butyl group, an isobutyl group; asubstituted alkyl group such as a chloromethyl group. Among them, analkyl group, in particular a non-substituted alkyl group is preferable,a methyl group or an ethyl group is more preferable. The hydroxyl groupmay be, but is not particularly limited to, a group generated byhydrolysis of a hydrolyzable group.

Preferably, R⁹⁵ is —OR wherein R is a substituted or unsubstituted C₁₋₃alkyl group, more preferably an ethyl group or a methyl group, inparticular a methyl group.

In the formula, R⁸⁶ is each independently at each occurrence a hydrogenatom or a lower alkyl group. The lower alkyl group is preferably analkyl group having 1-20 carbon atoms, more preferably an alkyl grouphaving 1-6 carbon atoms, further preferably a methyl group.

n2 is an integer of 1-3, preferably 2 or 3, more preferably 3,independently per unit —Y—SiR⁸⁵ _(n2)R⁸⁶ _(3−n2).

In the formula, R⁸³ is each independently at each occurrence a hydrogenatom or a lower alkyl group. The lower alkyl group is preferably analkyl group having 1-20 carbon atoms, more preferably an alkyl grouphaving 1-6 carbon atoms, further preferably a methyl group.

In the formula, p2 is each independently at each occurrence an integerof 0-3; q2 is each independently at each occurrence an integer of 0-3;r2 is each independently at each occurrence an integer of 0-3. The sumof p2, q2 and r2 is 3.

In a preferable embodiment, in R^(d)′ (when R^(d′) is absent, R^(d)) atthe terminal of R^(d), q2 is preferably 2 or more, for example 2 or 3,more preferably 3.

In a preferable embodiment, at least one of the terminal portion ofR^(d) may be —C(—Y—SiR⁸⁵ _(q2)R⁸⁶ _(r2))₂ or —C(—Y—SiR⁸⁵ _(q2)R⁸⁶_(r2))₃, preferably —C(—Y—SiR⁸⁵ _(q2)R⁸⁶ _(r2))₃. In the formula, theunit (—Y—SiR⁸⁵ _(q2)R⁸⁶ _(r2)) is preferably (—Y—SiR⁸⁵ ₃). In a furtherpreferable embodiment, all of the terminal portions of R^(d) are may be—C(—Y—SiR⁸⁵ _(q2)R⁸⁶ _(r2))₃, preferably —C(—Y—SiR⁸⁵ ₃)₃.

In the formula, R^(e) is each independently at each occurrence —Y—SiR⁸⁵_(n2)R⁸⁶ _(3−n2). Y, R⁸⁵, R³⁶ and n2 are as defined for R⁸².

In the formula, R¹ is each independently at each occurrence a hydrogenatom or a lower alkyl group. The lower alkyl group is preferably analkyl group having 1-20 carbon atoms, more preferably an alkyl grouphaving 1-6 carbon atoms, further preferably a methyl group.

In the formula, k2 is each independently at each occurrence an integerof 0-3; l2 is each independently at each occurrence an integer of 0-3;and m2 is each independently at each occurrence an integer of 0-3. Thesum of k2, l2 and m2 is 3.

In one embodiment, at least one k2 is 2 or 3, preferably 3.

In one embodiment, k2 is 2 or 3, preferably 3.

In one embodiment, l2 is 2 or 3, preferably 3.

In the formula (D1) and (D1), at least one q2 is 2 or 3, or at least onel is 2 or 3. That is, there are at least two —Y—SiR⁸⁵ _(2n)R⁸⁶ _(3−n2)groups in the formula.

The perfluoro(poly) ether group containing silane compound of theformula (D1) or the formula (D1) can be prepared by a combination ofknown methods. For example, a compound of the formula (D1′) wherein X isa divalent group can be prepared below, although the present inventionis not limited thereto.

A group containing a double bond (preferably allyl), and a halogen(preferably bromo) are introduced into polyol of HO—X—C(YOH)₃ (wherein Xand Y are each independently a divalent organic group) to obtain ahalide having a double bond of Hal-X—C(Y—O—R—CH═CH₂)₃ (wherein Hal ishalogen, for example Br, and R is a divalent organic group, for examplean alkylene group). Then, halogen at the terminal is reacted with aperfluoropolyether group containing alcohol of R^(PFPE)—OH (whereinR^(PFPE) is a perfluoropolyether group containing group.) to obtainR^(PFPE)—O—X—C(Y—O—R—CH═CH₂)₃. Then, —CH═CH₂ at the terminal is reactedwith HSiCl₃ and an alcohol or HSiR⁸⁵ ₃ to obtainR^(PFPE)—O—X—C(Y—O—R—CH₂—CH₂—SiR⁸⁵ ₃)₃.

The number average molecular weight of the perfluoropolyether groupcontaining silane compound of the formulae (A1), (A2), (B1), (B2), (C1),(C2), (D1) and (D2) may be, but not particularly limited to,5×10²-1×10⁵. The number average molecular weight may be preferably2,000-30,000, more preferably 3,000-10,000, further preferably3,000-8,000.

It is noted that, in the present invention, the “number averagemolecular weight” is measured by GPC (Gel Permeation Chromatography)analysis.

The number average molecular weight of the PFPE portion of theperfluoro(poly)ether group containing silane compound contained in thesurface-treating agent of the present invention may be, not particularlylimited to, preferably 1,500-30,000, more preferably 2,500-10,000,further preferably 3,000-8,000.

The fluorine containing oil used in the present invention is at leastone fluoropolyether compound of the general formula (O):

Rf¹-PFPE′-Rf²  (O)

Hereinbefore, the fluorine containing oil of the formula (O) isdescribed.

In the formula, Rf¹ is a C₁₋₁₆ alkyl group which may be substituted byone or more fluorine atoms.

Rf² is a C₁₋₁₆ alkyl group which may be substituted by one or morefluorine atoms, a fluorine atom or a hydrogen atom.

A “C₁₋₁₆ alkyl group which may be substituted by one or more fluorineatoms” in Rf¹ and Rf² is preferably an alkyl group having 1-16 carbonatoms which may be substituted one or more fluorine atoms, morepreferably CF₂H—C₁₋₁₅ fluoroalkylene group, further preferablyperfluoroalkyl group having 1-16 carbon atoms.

The perfluoroalkyl group having 1-16 carbon atoms may be straight orbranched, and preferably is a straight or branched perfluoroalkyl grouphaving 1-6 carbon atoms, in particular 1-3 carbon atoms, more preferablya straight perfluoroalkyl group having 1-3 carbon atoms, specifically—CF₃, —CF₂CF₃ or —CF₂CF₂CF₃.

In the formula, PFPE′ is—(OC₄F₈)_(a′)—(OC₃F₆)_(b′)—(OC₂F₄)_(c′)—(OCF₂)_(d′)—. Herein, a′, b′, c′and d′ are each independently 0 or an integer of 1 or more. The sum ofa′, b′, c′ and d′ is 1 or more. Preferably, a′, b′, c′ and d′ are eachindependently an integer of 0 or more and 300 or less, for example aninteger of 1 or more and 300 or less, more preferably each independentlyan integer of 0 or more and 100 or less. The sum of a′, b′, c′ and d′ ispreferably 5 or more, more preferably 10 or more, for example 10 or moreand 100 or less. The occurrence order of the respective repeating unitsin parentheses with the subscript a′, b′, c′ or d′ is not limited in theformula. Among these repeating units, the —(OC₄F₈)— group may be any of—(OCF₂CF₂CF₂CF₂)—, —(OCF(CF₃)CF₂CF₂)—, —(OCF₂CF(CF₃)CF₂)—,—(OCF₂CF₂CF(CF₃))—, —(OC(CF₃)₂CF₂)—, —(OCF₂C(CF₃)₂)—,—(OCF(CF₃)CF(CF₃))—, —(OCF(C₂F₅)CF₂)— and —(OCF₂CF(C₂F₅))—, preferably—(OCF₂CF₂CF₂CF₂)—. The —(OC₃F₆)— group may be any of —(OCF₂CF₂CF₂)—,—(OCF(CF₃)CF₂)— and —(OCF₂CF(CF₃))—, preferably —(OCF₂CF₂CF₂)—. The—(OC₂F₄)— group may be any of —(OCF₂CF₂)— and —(OCF(CF₃))—, preferably—(OCF₂CF₂)—.

Examples of the fluorine containing oil of the above general formula (O)include a compound of any of the following general formulae (01) and(02) (may be one compound or a mixture of two or more compounds):

R²¹—(OCF₂CF₂CF₂)_(b′)—R²²  (O1)

R²¹—(OCF₂CF₂CF₂CF₂)_(a″)—(OCF₂CF₂CF₂)_(b″)—(OCF₂CF₂)_(c″)—(OCF₂)_(d″)—R²²  (O2)

wherein:

R²¹ is an alkyl group having 1-16 carbon atoms which may be substitutedby one or more fluorine atoms;

R²² is an alkyl group having 1-16 carbon atoms which may be substitutedby one or more fluorine atoms, a fluorine atom or a hydrogen atom;

in the formula (O1), b″ is an integer of 1 or more and 100 or less;

in the formula (O2), a″ and b″ are each independently an integer of 0 ormore and 30 or less, for example an integer of 1 or more and 30 or lessand c″ and d″ are each independently an integer of 1 or more and 300 orless; and

the occurrence order of the respective repeating units in parentheseswith the subscript a″, b″, c″ or d″ is not limited in the formula.

A content of the fluorine containing oil having high molecular weightamong the fluorine containing oil of the formula (O) contained in thesurface treating agent of the present invention is 10 mol % or less,preferably 7 mol % or less, more preferably 5 mol % or less, furtherpreferably 3 mol % or less, further more preferably 2 mol % or less.Further more preferably, the surface treating agent of the presentinvention contains substantively no fluorine containing oil having highmolecular weight. By decreasing the fluorine containing oil having highmolecular weight, higher transparency and higher friction durability canbe achieved.

In one embodiment, the fluorine containing oil having high molecularweight in the fluorine containing oil contained in the surface treatingagent of the present invention is the fluorine containing oil having amolecular weight of 3.0 or more times, preferably 2.5 or more times,more preferably 2.0 or more times, further preferably 1.8 or more timeshigher than the number average molecular weight of the total of thefluorine containing oils. By decreasing the fraction containing thefluorine containing oil having lower molecular weight, highertransparency can be achieved.

In a preferable embodiment, among the fluorine containing oil of theformula (O) contained in the surface treating agent of the presentinvention, the content of the fluorine containing oil having a molecularweight of 2.0 or more times higher than the number average molecularweight of the total of the fluorine-containing oils is 10 mol % or less,preferably 7 mol % or less, more preferably 5 mol % or less, furtherpreferably 3 mol % or less, further more preferably 2 mol % or less.

In a more preferably embodiment, among the fluorine containing oil ofthe formula (O) contained in the surface treating agent of the presentinvention, the content of the fluorine containing oil having a molecularweight of 1.8 or more times higher than the number average molecularweight of the total of the fluorine-containing oils is 10 mol % or less,preferably 9 mol % or less, more preferably 8 mol % or less, furtherpreferably 7 mol % or less, further more preferably 5 mol % or less,particularly preferably 3 mol % or less, particularly more preferably 2mol % or less.

In the above embodiment, a number average molecular weight of thefluorine containing oil may be preferably 1500 or more and 30,000 orless, more preferably 2,000 or more and 10,000 or less, furtherpreferably 2,000 or more and 6,000 or less, for example 2,500 or more or3,000 or more and 6,000 or less or 5,500 or less.

In another embodiment, among the fluorine containing oil of the formula(O) contained in the surface treating agent of the present invention,the fluorine containing oil having high molecular weight is the fluorinecontaining oil having a molecular weight of 10,000 or more, preferably8,000 or more, more preferably 5,000 or more. By decreasing the fluorinecontaining oil fraction of the fluorine containing oil having lowermolecular weight, higher transparency can be obtained.

In a preferable embodiment, among the fluorine containing oil of theformula (O) contained in the surface treating agent of the presentinvention, the content of the fluorine containing oil having a molecularweight of 5,000 or more may be 10 mol % or less, preferably 7 mol % orless, more preferably 5 mol % or less, further preferably 3 mol % orless, further more preferably 2 mol % or less.

In the above embodiment, a number average molecular weight of thefluorine containing oil may be preferably 1,500 or more and 8,000 orless, more preferably 2,000 or more and 7,000 or less, furtherpreferably 2,000 or more and 5,500 or less, for example 2,000 or moreand 4,500 or less.

In a further other embodiment, the dispersity (weight average molecularweight (Mw)/number average molecular weight (Mn)) of the fluorinecontaining oil contained in the surface treating agent of the presentinvention is 1.00 or more and 1.30 or less, preferably 1.00 or more and1.20 or less, more preferably 1.00 or more and 1.10 or less. Bydecreasing the dispersity of the fluorine containing oil, highertransparency and higher friction durability can be obtained.

In the above embodiment, a number average molecular weight of thefluorine containing oil may be preferably 1,500 or more and 10,000 orless, more preferably 1,500 or more and 8,000 or less, furtherpreferably 1,500 or more and 5,500 or less, for example 2,000 or moreand 5,500 or less.

In a preferable embodiment, with respect to the fluorine containing oilof the formula (O) contained in the surface treating agent of thepresent invention, the number average molecular weight is 1,500 or moreand 10,000 or less, preferably 1,500 or more and 8,000 or less, morepreferably 1,500 or more and 5,500 or less, for example 2,000 or moreand 5,500 or less; the dispersity is 1.00 or more and 1.20 or less,preferably 1.00 or more and 1.10 or less, more preferably 1.00 or moreand 1.05 or less; and the content of the fluorine containing oil havinga molecular weight of 10,000 or more, preferably 8,000 or more, morepreferably 5,000 or more is 10 mol % or less, preferably 7 mol % orless, more preferably 5 mol % or less, further preferably 3 mol % orless, further more preferably 2 mol % or less with respect to the totalthe fluorine containing oils.

It is noted that the content of a fluorine containing oil having theparticular molecular weight among the fluorine containing oils containedin the surface treating agent can be measured by GPC (Gel PermeationChromatography) analysis. The GPC measurement can be performed forexample by using GPCmax provided with TDA-302 (HPLC system: manufacturedby Malvern Instruments) as a detector.

The fluorine containing oil used in the surface treating agent of thepresent invention can be obtained as a commercially available fluorinecontaining oil or can be obtained by distilling the commerciallyavailable fluorine containing oil. The fluorine containing oil used inthe surface treating agent of the present invention can be synthesizeddepending on the required properties.

The fluorine-containing oil may be contained in the surface-treatingagent of the present invention, for example, 5-95% by mass, preferably10-90% by mass, more preferably 20-80% by mass, further preferably 30-70h. by mass with respect to 100 parts by mass of the perfluoro(poly)ethergroup containing silane compound and the fluorine containing oil (as thetotal mass when two or more compounds are used; hereinafter the sameshall apply).

The surface treating agent may comprise other components in addition tothe perfluoro(poly)ether group containing silane compound and thefluorine containing oil. Examples of the other components include, butare not particularly limited to, for example, a (non-reactive) siliconecompound which may be also understood as a silicone oil (hereinafterreferred to as “a silicone oil”), a catalyst, and the like.

Examples of the above-mentioned silicone oil include, for example, aliner or cyclic silicone oil having 2,000 or less siloxane bonds. Theliner silicone oil may be so-called a straight silicone oil and amodified silicon oil. Examples of the straight silicone oil includedimethylsilicone oil, methylphenylsilicone oil, andmethylhydrogensilicone oil. Examples of the modified silicone oilinclude that which is obtained by modifying a straight silicone oil withalkyl, aralkyl, polyether, higher fatty acid ester, fluoroalkyl, amino,epoxy, carboxyl, alcohol, or the like. Examples of the cyclic siliconeoil include, for example, cyclic dimethylsiloxane oil.

The silicone oil may be contained in the surface-treating agent of thepresent invention, for example, at 0-300 parts by mass, preferably 0-200parts by mass with respect to 100 parts by mass of theperfluoro(poly)ether group containing silane compound and the fluorinecontaining oil (as the total mass when two or more compounds are used;hereinafter the same shall apply).

The silicone oil contributes to increasing of surface slip property ofthe surface-treating layer.

Examples of the above-mentioned catalyst include an acid (for example,acetic acid, trifluoroacetic acid, etc.), a base (for example, ammonia,triethylamine, diethylamine, etc.), a transition metal (for example, Ti,Ni, Sn, etc.), and the like.

The catalyst facilitates hydrolysis and dehydration-condensation of theperfluoro(poly)ether group containing silane compound to facilitate aformation of the surface-treating layer.

The surface treating agent may be diluted with a solvent. Examples ofthe solvent include, but are not particularly limited to, for example, asolvent selected from the group consisting of perfluorohexane,CF₃CF₂CHCl₂, CF₃CH₂CF₂CH₃, CF₃CHFCHFC₂F₅,1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorooctane,1,1,2,2,3,3,4-heptafluorocyclopentane (ZEORORA H (trade name), etc.),C₄F₉OCH₃, C₄F₉OC₂H₅, CF₃CH₂OCF₂CHF₂, C₆F₁₃CH═CH₂, xylene hexafluoride,perfluorobenzene, methyl pentadecafluoroheptyl ketone, trifluoroethanol,pentafluoropropanol, hexafluoroisopropanol, HCF₂CF₂CH₂OH, methyltrifluoromethanesulfonate, trifluoroacetic acid andCF₃O(CF₂CF₂O)_(m)(CF₂O)CF₂CF₃ [wherein m and n are each independently aninteger of 0 or more and 1000 or less, the occurrence order of therespective repeating units in parentheses with the subscript m or n isnot limited in the formula, with the proviso that the sum of m and n is1 or more.], 1,1-dichloro-2,3,3,3-tetrafluoro-1-propene,1,2-dichloro-1,3,3,3-tetrafluoro-1-propene,1,2-dichloro-3,3,3-trichloro-1-propene,1,1-dichloro-3,3,3-trichloro-1-propene,1,1,2-trichloro-3,3,3-trichloro-1-propene,1,1,1,4,4,4-hexafluoro-2-butene. These solvents may be used alone or asa mixture of 2 or more compound.

The surface-treating agent of the present invention can provide a basematerial with water-repellency, oil-repellency, antifouling property,waterproof property and high friction durability, and can be suitablyused as an antifouling-coating agent or a water-proof coating agent,although the present invention is not particularly limited thereto.

The surface-treating agent of the present invention is impregnated intoa porous material, for example, a porous ceramic material, a metal fiberfor example that obtained by solidifying a steel wool to obtain apellet. The pellet can be used, for example, in vacuum deposition.

Next, the article of the present invention will be described.

The article of the present invention comprises a base material and alayer (surface-treating layer) which is formed from the surface-treatingagent of the present invention on the surface of the base material.

The surface treating layer of the article of the present inventioncontains lower content of the fluorine containing oil having highmolecular weight. In particular, among the fluorine containing oil ofthe formula (O), the content of the fluorine containing oil having highmolecular weight is 10 mol-% or less, preferably 7 mol % or less, morepreferably 5 mol or less, further preferably 3 mol % or less.

The surface treating layer obtained by using the surface treating agentof the present invention has high transparency. For example, the hazevalue may be 0.35% or less, preferably 0.30% or less, more preferably0.28% or less, further preferably 0.25% or less, further more preferably0.20% or less. The haze value can be measured by a commerciallyavailable haze meter.

Therefore, in the article of the present invention, when the basematerial is transparent, for example when the article is an opticalmember, the haze value of the article itself may be 0.35% or less,preferably 0.30% or less, more preferably 0.28% or less, furtherpreferably 0.25% or less, further more preferably 0.20% or less.

The thickness of the surface-treating layer is not specifically limited.For the optical member, the thickness of the surface-treating layer iswithin the range of 1-50 nm, preferably 1-30 nm, more preferably 1-15nm, in view of optical performance, surface slip property, frictiondurability and antifouling property.

The article of the present invention can be produced, for example, asfollows.

Firstly, the base material is provided. The base material usable in thepresent invention may be composed of any suitable material such as aglass, a sapphire glass, a resin (may be a natural or synthetic resinsuch as a common plastic material, and may be in form of a plate, afilm, or others), a metal (may be a simple substance of a metal such asaluminum, copper, or iron, or a complex such as alloy or the like), aceramic, a semiconductor (silicon, germanium, or the like), a fiber (afabric, a non-woven fabric, or the like), a fur, a leather, a wood, apottery, a stone, an architectural member or the like. The base materialis preferably a glass or a sapphire glass.

As the glass, a soda-lime glass, an alkali aluminosilicate glass, aborosilicate glass, a non-alkaline glass, a crystal glass, a quartzglass is preferable, a chemically strengthened soda-lime glass, achemically strengthened alkali aluminosilicate glass, and a chemicallystrengthened borosilicate glass are more preferable.

As the resin, an acrylic resin or a polycarbonate resin are preferable.

For example, when an article to be produced is an optical member, amaterial constituting the surface of the base material may be a materialfor an optical member, for example, a glass or a transparent plastic.For example, when an article to be produced is an optical member, anylayer (or film) such as a hard coating layer or an antireflection layermay be formed on the surface (outermost layer) of the base material. Asthe antireflection layer, either a single antireflection layer or amulti antireflection layer may be used. Examples of an inorganicmaterial usable in the antireflection layer include SiO₂, SiO, ZrO₂,TiO₂, TiO, Ti₂O₃, Ti₂O₅, Al₂O₃, Ta₂O₅, CeO₂, MgO, Y₂O₃, SnO₂, MgF₂, WO₃,and the like. These inorganic materials may be used alone or incombination with two or more (for example, as a mixture). When multiantireflection layer is formed, preferably, SiO₂ and/or SiO are used inthe outermost layer. When an article to be produced is an optical glasspart for a touch panel, it may have a transparent electrode, forexample, a thin layer comprising indium tin oxide (ITO), indium zincoxide, or the like on a part of the surface of the base material(glass). Furthermore, the base material may have an insulating layer, anadhesive layer, a protecting layer, a decorated frame layer (I-CON), anatomizing layer, a hard coating layer, a polarizing film, a phasedifference film, a liquid crystal display module, and the like,depending on its specific specification.

The shape of the base material is not specifically limited. The regionof the surface of the base material on which the surface-treating layershould be formed may be at least a part of the surface of the basematerial, and may be appropriately determined depending on use, thespecific specification, and the like of the article to be produced.

The base material may be that of which at least the surface consists ofa material originally having a hydroxyl group. Examples of such materialinclude a glass, in addition, a metal on which a natural oxidized filmor a thermal oxidized film is formed (in particular, a base metal), aceramic, a semiconductor, and the like. Alternatively, as in a resin,when the hydroxyl groups are present but not sufficient, or when thehydroxyl group is originally absent, the hydroxyl group can beintroduced on the surface of the base material, or the number of thehydroxyl group can be increased by subjecting the base material to anypretreatment. Examples of the pretreatment include a plasma treatment(for example, corona discharge) or an ion beam irradiation. The plasmatreatment may be suitably used to introduce the hydroxyl group into orincrease it on the surface of the base material, further, to clarify thesurface of the base material (remove foreign materials, and the like).Alternatively, other examples of the pretreatment include a methodwherein a monolayer of a surface adsorbent having a carbon-carbonunsaturated bond group is formed on the surface of the base material byusing a LB method (Langmuir-Blodgett method) or a chemical adsorptionmethod beforehand, and then, cleaving the unsaturated bond under anatmosphere of oxygen and nitrogen.

Alternatively, the base material may be that of which at least thesurface consists of a material comprising other reactive group such as asilicon compound having one or more Si—H groups or alkoxysilane.

Next, the film of the above surface-treating agent of the presentinvention is formed on the surface of the base material, and the film ispost-treated, as necessary, and thereby the surface-treating layer isformed from the surface-treating agent.

The formation of the film of the surface-treating agent of the presentinvention can be performed by applying the above surface-treating agenton the surface of the base material such that the surface-treating agentcoats the surface. The method of coating is not specifically limited.For example, a wet coating method or a dry coating method can be used.

Examples of the wet coating method include dip coating, spin coating,flow coating, spray coating, roll coating, gravure coating, and asimilar method.

Examples of the dry coating method include deposition (usually, vacuumdeposition), sputtering, CVD and a similar method. The specific examplesof the deposition method (usually, vacuum deposition) include resistanceheating, electron beam, high-frequency heating using microwave, etc.,ion beam, and a similar method. The specific examples of the CVD methodinclude plasma-CVD, optical CVD, thermal CVD and a similar method. Thedeposition method is will be described below in more detail.

Additionally, coating can be performed by an atmospheric pressure plasmamethod.

When the wet coating method is used, the surface-treating agent of thepresent invention is diluted with a solvent, and then it is applied tothe surface of the base material. In view of stability of thesurface-treating agent of the present invention and volatile property ofthe solvent, the following solvents are preferably used: a C₅₋₁₂aliphatic perfluorohydrocarbon (for example, perfluorohexane,perfluoromethylcyclohexane and perfluoro-1,3-dimethylcyclohexane); anaromatic polyfluorohydrocarbon (for example,bis(trifluoromethyl)benzene); an aliphatic polyfluorohydrocarbon (forexample, C₆F₁₃CH₂CH₃ (for example, ASAHIKLIN (registered trademark)AC-6000 manufactured by Asahi Glass Co., Ltd.),1,1,2,2,3,3,4-heptafluorocyclopentane (for example, ZEORORA (registeredtrademark) H manufactured by Nippon Zeon Co., Ltd.); hydrofluorocarbon(HFC) (for example, 1,1,1,3,3-pentafluorobutane (HFC-365mfc));hydrochlorofluorocarbon (for example, HCFC-225 (ASAHIKLIN (registeredtrademark) AK225)); a hydrofluoroether (HFE) (for example, an alkylperfluoroalkyl ether such as perfluoropropyl methyl ether (C₃F₇OCH₃)(for example, Novec (trademark) 7000 manufactured by Sumitomo 3M Ltd.),perfluorobutyl methyl ether (C₄F₉OCH₃) (for example, Novec (trademark)7100 manufactured by Sumitomo 3M Ltd.), perfluorobutyl ethyl ether(C₄F₉₀C₂H₅) (for example, Novec (trademark) 7200 manufactured bySumitomo 3M Ltd.), and perfluorohexyl methyl ether (C₂F₅CF(OCH₃)C3F₇)(for example, Novec (trademark) 7300 manufactured by Sumitomo 3M Ltd.)(the perfluoroalkyl group and the alkyl group may be liner orbranched)), or CF₃CH₂OCF₂CHF₂ (for example, ASAHIKLIN (registeredtrademark) AE-3000 manufactured by Asahi Glass Co., Ltd.),1,2-dichloro-1,3,3,3-tetrafluoro-1-propene (for example, VERTREL(registered trademark) Sion manufactured by Du Pont-MitsuiFluorochemicals Co., Ltd.) and the like. These solvents may be usedalone or as a mixture of 2 or more compound. Among them, thehydrofluoroether is preferable, perfluorobutyl methyl ether (C₄F₉OCH₃)and/or perfluorobutyl ethyl ether (C₄F₉OC₂H₅) are particularlypreferable. Furthermore, the solvent can be mixed with another solvent,for example, to adjust solubility of the perfluoro(poly)ether groupcontaining silane compound.

When the dry coating method is used, the surface-treating agent of thepresent invention may be directly subjected to the dry coating method,or may be diluted with a solvent, and then subjected to the dry coatingmethod.

The formation of the film is preferably performed so that thesurface-treating agent of the present invention is present together witha catalyst for hydrolysis and dehydration-condensation in the coating.Simply, when the wet coating method is used, after the surface-treatingagent of the present invention is diluted with a solvent, and just priorto applying it to the surface of the base material, the catalyst may beadded to the diluted solution of the surface-treating agent of thepresent invention. When the dry coating method is used, thesurface-treating agent of the present invention to which a catalyst hasbeen added is used itself in deposition (usually, vacuum deposition), orpellets may be used in the deposition (usually, the vacuum deposition),wherein the pellets is obtained by impregnating a porous metal such asiron or copper with the surface-treating agent of the present inventionto which the catalyst has been added.

As the catalyst, any suitable acid or base can be used. As the acidcatalyst, for example, acetic acid, formic acid, trifluoroacetic acid,or the like can be used. As the base catalyst, for example, ammonia, anorganic amine, or the like can be used.

Next, the film is post-treated as necessary. This post-treatment is, butnot limited to, a treatment in which water supplying and dry heating aresequentially performed, in more particular, may be performed as follows.

After the film of the surface-treating agent of the present invention isformed on the surface of the base material as mentioned above, water issupplied to this film (hereinafter, referred to as precursor coating).The method of supplying water may be, for example, a method using dewcondensation due to the temperature difference between the precursorcoating (and the base material) and ambient atmosphere or spraying ofwater vapor (steam), but not specifically limited thereto.

It is considered that, when water is supplied to the precursor coating,water acts on a hydrolyzable group bonding to Si present in theperfluoro(poly)ether group containing silane compound in thesurface-treating agent of the present invention, thereby enabling rapidhydrolysis of the compound.

The supplying of water may be performed under an atmosphere, forexample, at a temperature of 0-250° C., preferably 60° C. or more, morepreferably 100° C. or more and preferably 180° C. or less, morepreferably 150° C. By supplying water at such temperature range,hydrolysis can proceed. The pressure at this time is not specificallylimited but simply may be ambient pressure.

Then, the precursor coating is heated on the surface of the basematerial under a dry atmosphere over 60° C. The method of dry heatingmay be to place the precursor coating together with the base material inan atmosphere at a temperature over 60° C., preferably over 100° C., andfor example, of 250° C. or less, preferably of 180° C. or less, and atunsaturated water vapor pressure, but not specifically limited thereto.The pressure at this time is not specifically limited but simply may beambient pressure.

Under such atmosphere, between the PFPE containing silane compound ofthe present inventions, the groups bonding to Si after hydrolysis arerapidly dehydration-condensed with each other. Furthermore, between thecompound and the base material, the group bonding to Si in the compoundafter hydrolysis and a reactive group present on the surface of the basematerial are rapidly reacted, and when the reactive group present on thesurface of the base material is a hydroxyl group,dehydration-condensation is caused. As the result, the bond between theperfluoro(poly)ether group containing silane compound and the basematerial is formed.

The above supplying of water and dry heating may be sequentiallyperformed by using a superheated water vapor.

As mentioned above, the post-treatment can be performed. It is notedthat though the post-treatment may be performed in order to furtherincrease friction durability, it is not essential in the producing ofthe article of the present invention. For example, after applying thesurface-treating agent to the surface of the base material, it may beenough to only stand the base material.

As described above, the surface-treating layer derived from the film ofthe surface-treating agent of the present invention is formed on thesurface of the base material to produce the article of the presentinvention. The surface-treating layer thus formed has highertransparency, high surface slip property and high friction durability.Furthermore, this surface-treating layer may have water-repellency,oil-repellency, antifouling property (for example, preventing fromadhering a fouling such as fingerprints), waterproof property(preventing the ingress of water into an electrical member, and thelike), surface slip property (or lubricity, for example, wiping propertyof a fouling such as fingerprints and excellent tactile feeling in afinger) depending on a composition of the surface-treating agent used,in addition to high friction durability, thus may be suitably used as afunctional thin film.

The article having the surface-treating layer obtained according to thepresent invention is not specifically limited to, but may be an opticalmember. Examples of the optical member include the followings: displayssuch as a cathode ray tube (CRT; for example, TV, personal computermonitor), a liquid crystal display, a plasma display, an organic ELdisplay, an inorganic thin-film EL dot matrix display, a rear projectiondisplay, a vacuum fluorescent display (VFD), a field emission display(FED; Field Emission Display), or a front surface protective plate, anantireflection plate, a polarizing plate, or an anti-glare plate ofthese display, or these whose surface is subjected to antireflectiontreatment; lens of glasses, or the like; a touch panel sheet of aninstrument such as a mobile phone or a personal digital assistance; adisk surface of an optical disk such as a Blu-ray disk, a DVD disk, aCD-R or MO; an optical fiber, and the like; a display surface of aclock.

Other article having the surface-treating layer obtained according tothe present invention may be also a ceramic product, a painted surface,a cloth product, a leather product, a medical product and a plaster.

The article having the surface-treating layer obtained according to thepresent invention may be also a medical equipment or a medical material.

Hereinbefore, the article produced by using the surface-treating agentof the present invention is described in detail. It is noted that anapplication, a method for using or a method for producing the articleare not limited to the above exemplification.

EXAMPLES

The surface-treating agent of the present invention will be described indetail through Examples, although the present invention is not limitedto Examples. It is noted that in Examples, all chemical formulaedescribed below mean an average composition.

Compound (A) and Compound (B) were used as a perfluoro(poly)ether groupcontaining silane compound.

wherein m is an integer of 1-6.

Each of three perfluoropolyether compounds (Compounds (C)-(E)) havingdifferent molecular weight distribution were used as a the fluorinecontaining oil.

Structure:

CF₃O(CF₂O)_(p)(CF₂CF₂O)_(q)CF₃

wherein p and q is given values.

Compound (C)

Compound (C) is obtained as a fraction at 194° C.-320° C. bymolecular-distilling FOMBLIN M03 (manufactured by Solvay SpecialtyPolymers Japan K.K.) under 60-70 Pa.

Compound (D)

FOMBLIN M03 (manufactured by Solvay Specialty Polymers Japan K.K.)

Compound (E)

FOMBLIN Z03 (manufactured by Solvay Specialty Polymers Japan K.K.)

Compound (F)

4:1 mixture of Compound (C) and Compound (D)

Compound (G) 1:1 mixture of Compound (C) and Compound (D)

Compound (H)

3:7 mixture of Compound (C) and Compound (D)

With respect to Compounds (C)-(H), the weight average molecular weight(Mw), number average molecular weight (Mn) and dispersity (Mw/Mn) weremeasured by gel permeation chromatography (GPC). The measurement of GPCwere performed under the following conditions. Mw, Mn, Mw/Mn and thecontents of the fluorine containing oil having x times Mn are shown inTable 1.

Equipment: GPCmax (manufactured by HPLC system: Malvern Instruments)

Mobile phase: Mixed solvent of AK-225 (manufactured by Asahi Glass Co.,Ltd, ASAHIKLIN AK-225) and hexafluoroisopropanol (HFIP)

(AK-225/HFIP=90/10 (volume ratio))

Analytical column: Two Shodex KF-806L were connected in series.

Standard sample for measurement of molecular weight: Threeperfluoropolyether compounds having Mn of 1000-10000 Detector:

Mobile phase flow rate: 0.7 mL/min

Column temperature: 30° C.

TABLE 1 Content of compounds Content of compounds having a molecularhaving a molecular weight more than x weight of 5000 or times Mn (mol %)Mw Mn Mw/Mn more (mol %) x = 3.0 x = 2.0 x = 1.8 Compound 3,087 2,9041.063 2.7 0.8 1.1 2.0 (C) Compound 4,400 3,026 1.432 12.7 7.5 10.5 11.5(D) Compound 4,411 3,275 1.347 17.1 7.4 11.3 12.8 (E) Compound 3,0753,506 1.140 8.8 0.9 2.4 6.6 (F) Compound 3,098 3,665 1.183 10.3 2.1 4.27.1 (G) Compound 3,123 3,839 1.230 12.6 3.6 6.1 8.2 (H)

Preparation of the Surface Treating Agent:

Example 1

Compound (A) and Compound (C) were dissolved in hydrofluoroether(manufactured by 3M Company, Novec HFE7200) at the mass ratio of 2:1such that concentration (the total of Compound (A) and Compound (C)) was0.1 wt % to prepare the surface treating agent 1.

Example 2

Compound (A) and Compound (C) were dissolved in hydrofluoroether(manufactured by 3M Company, Novec HFE7200) at the mass ratio of 1:1such that concentration (the total of Compound (A) and Compound (C)) was0.1 wt % to prepare the surface treating agent 2.

Example 3

Compound (B) and Compound (C) were dissolved in hydrofluoroether(manufactured by 3M Company, Novec HFE7200) at the mass ratio of 1:1such that concentration (the total of Compound (B) and Compound (C)) was0.1 wt % to prepare the surface treating agent 3.

Example 4

Compound (A) and Compound (F) were dissolved in hydrofluoroether(manufactured by 3M Company, Novec HFE7200) at the mass ratio of 1:1such that concentration (the total of Compound (A) and Compound (F)) was0.1 wt % to prepare the surface treating agent 4.

Example 5

Compound (A) and Compound (G) were dissolved in hydrofluoroether(manufactured by 3M Company, Novec HFE7200) at the mass ratio of 1:1such that concentration (the total of Compound (A) and Compound (G)) was0.1 wt % to prepare the surface treating agent 5.

Example 6

Compound (A) and Compound (H) were dissolved in hydrofluoroether(manufactured by 3M Company, Novec HFE7200) at the mass ratio of 1:1such that concentration (the total of Compound (A) and Compound (H)) was0.1 wt % to prepare the surface treating agent 6.

Comparative Example 1

Compound (A) and Compound (D) were dissolved in hydrofluoroether(manufactured by 3M Company, Novec HFE7200) at the mass ratio of 1:1such that concentration (the total of Compound (A) and Compound (D)) was0.1 wt % to prepare the surface treating agent 7.

Comparative Example 2

Compound (A) and Compound (E) were dissolved in hydrofluoroether(manufactured by 3M Company, Novec HFE7200) at the mass ratio of 1:1such that concentration (the total of Compound (A) and Compound (E)) was0.1 wt % to prepare the surface treating agent 8.

Formation of the surface treating layer (spray treatment):

Next, Surface treating agents 1-5 above prepared was uniformlyspray-coated on a chemical strengthening glass (Gorilla glassmanufactured by Corning Incorporated; thickness: 0.7 mm) by using thecommercial spray coating equipment equipped with a two-fluid nozzle. Thesurface of the chemical strengthening glass was subjected to a plasmatreatment using an atmospheric pressure plasma generator just prior tospray coating. A coating amount of the surface-treating agent was 0.2 m1per one plate of chemical strengthening glass (55 mm×100 mm). Then, thechemical strengthening glass having the spray treated layer was stoodunder an atmosphere where temperature is 20° C. and humidity is 65% for48 hours. Thus, the spray treated layer was cured and thesurface-treating layer was formed.

Evaluation

Evaluation of Friction Durability

A static water contact angle of the surface-treating layers formed onthe surface of the base material from the surface treating agents 1-8was measured. The static water contact angle was measured for 1 μL ofwater by using a contact angle measuring instrument (manufactured byKYOWA INTERFACE SCIENCE Co., Ltd.).

Firstly, as an initial evaluation, the static water contact angle of thesurface-treating layer of which the surface had not still contacted withanything after formation thereof was measured (the number of rubbing iszero).

Then, as an evaluation of the friction durability, a steel wool frictiondurability evaluation was performed. Specifically, the base material onwhich the surface-treating layer was formed was horizontally arranged,and then, a steel wool (grade No. 0000, dimensions: 5 mm×10 mm×10 mm)was contacted with the exposed surface of the surface-treating layer anda load of 1000 gf was applied thereon. Then, the steel wool was shuttledwhile applying the load at the rate 140 mm/sec. The static water contactangle was measured per 1,000 times. The evaluation was stopped when themeasured value of the contact angle became to be less than 100 degree.The number of reciprocation is shown in the following table at the timeof becoming the contact angle less than 100 degree.

Evaluation of Haze value

With respect to the surface treating layers formed on the surface of thebase material from the surface treating agents 1-8, haze values weremeasured by Haze meter (Manufactured by NIPPON DENSHOKU INDUSTRIES CO.,LTD NDH-7000). The results are shown in Table 2.

TABLE 2 Friction Haze Mixture durability value ratio (times) (%) Example1 Compound (A)/ 2:1 20,000 0.18 Compound (C) Example 2 Compound (A)/ 1:116,000 0.17 Compound (C) Example 3 Compound (B)/ 1:1 9,000 0.20 Compound(C) Example 4 Compound (A)/ 1:1 16,000 0.19 Compound (F) Example 5Compound (A)/ 1:1 15,000 0.20 Compound (G) Example 6 Compound (A)/ 1:114,000 0.26 Compound (H) Comparative Compound (A)/ 1:1 7,000 0.40Example 1 Compound (D) Comparative Compound (A)/ 1:1 8,000 0.30 Example2 Compound (E)

From table 2, in Examples 1-3 using the surface treating agentcontaining substantively no the fluorine containing oil having highermolecular weight, it was confirmed that haze value was lower than thatin Comparative Examples 1-2. In Examples 1-3 using the surface treatingagent containing substantively no the fluorine containing oil havinghigher molecular weight, it was confirmed that friction durability washigher than that in Comparative Examples 1-2. In particular, it wasconfirmed that the surface treating layer in Example 1 has lower hazevalue and higher friction durability.

INDUSTRIAL APPLICABILITY

The present invention is suitably applied for forming a surface-treatinglayer on a surface of various base materials, in particular, an opticalmember in which transparency is required.

1. A surface-treating agent comprising (1) at least oneperfluoro(poly)ether group containing silane compound of any of theformulae (A1), (A2), (B1), (B2), (C1), (C2), (D1) and (D2):

wherein: PFPE is each independently at each occurrence a group of theformula:—(OC₄F₈)_(a)—(OC₃F₆)_(b)—(OC₂F₄)_(c)—(OCF₂)_(d)— wherein a, b, c and dare each independently an integer of 0-200, the sum of a, b, c and d isat least one, and the occurrence order of the respective repeating unitsin parentheses with the subscript a, b, c or d is not limited in theformula; Rf is each independently at each occurrence an alkyl grouphaving 1-16 carbon atoms which may be substituted by one or morefluorine atoms; R¹ is each independently at each occurrence a hydroxylgroup or a hydrolyzable group; R² is each independently at eachoccurrence a hydrogen atom or an alkyl group having 1-22 carbon atoms;R¹¹ is each independently at each occurrence a hydrogen atom or ahalogen atom; R¹² is each independently at each occurrence a hydrogenatom or a lower alkyl group; n1 is, independently per a unit(—SiR_(n1)R² _(3−n1)), an integer of 0-3; at least one n1 is an integerof 1-3 in the formulae (A1), (A2), (B1) and (B2); X¹ is eachindependently a single bond or a 2-10 valent organic group; X² is eachindependently at each occurrence a single bond or a divalent organicgroup; t is each independently at each occurrence an integer of 1-10; αis each independently an integer of 1-9; α′ is each independently aninteger of 1-9; X⁵ is each independently a single bond or a 2-10 valentorganic group; β is each independently an integer of 1-9; β′ is eachindependently an integer of 1-9; X⁷ is each independently a single bondor a 2-10 valent organic group; γ is each independently an integer of1-9; γ′ is each independently an integer of 1-9; R^(a) is eachindependently at each occurrence —Z¹—SiR⁷¹ _(p1)R⁷² _(q1)R⁷³ _(r1); Z¹is each independently at each occurrence an oxygen atom or a divalentorganic group; R⁷¹ is each independently at each occurrence R^(a′);R^(a′) has the same definition as that of R^(a); in R^(a), the number ofSi atoms which are straightly linked via the Z¹ group is up to five; R⁷²is each independently at each occurrence a hydroxyl group or ahydrolyzable group; R⁷³ is each independently at each occurrence ahydrogen atom or a lower alkyl group; p1 is each independently at eachoccurrence an integer of 0-3; q1 is each independently at eachoccurrence an integer of 0-3; r1 is each independently at eachoccurrence an integer of 0-3; at least one q1 is an integer of 1-3 inthe formula (C1) and (C2); R^(b) is each independently at eachoccurrence a hydroxyl group or a hydrolyzable group; R^(c) is eachindependently at each occurrence a hydrogen atom or a lower alkyl group;k1 is each independently at each occurrence an integer of 1-3; l1 iseach independently at each occurrence an integer of 0-2; m1 is eachindependently at each occurrence an integer of 0-2; the sum of k1, l1and m1 is 3 in each unit in parentheses with the subscript γ; X⁹ is eachindependently a single bond or a 2-10 valent organic group; δ is eachindependently an integer of 1-9; δ′ is each independently an integer of1-9; R^(d) is each independently at each occurrence —Z—CR⁸¹ _(p2)R⁸²_(q2)R⁸³ _(r2); Z⁸¹ is each independently at each occurrence an oxygenatom or a divalent organic group; R^(d′) is each independently at eachoccurrence R^(d); R⁸¹ has the same definition as that of R^(d); inR^(d), the number of C atoms which are straightly linked via the Z²group is up to five; R⁸² is each independently at each occurrence—Y—SiR⁸⁵ _(n2)R⁸⁶ _(3−n2); Y is each independently at each occurrence adivalent organic group; R⁸⁵ is each independently at each occurrence ahydroxyl group or a hydrolyzable group; R⁸⁶ is each independently ateach occurrence a hydrogen atom or a lower alkyl group; n2 is an integerof 1-3 independently per unit (—Y—SiR⁸⁵ _(n2)R⁸⁶ _(3−n2)); in formulae(D1) and (D2), at least one n2 is an integer of 1-3; R⁸³ is eachindependently at each occurrence a hydrogen atom or a lower alkyl group;p2 is each independently at each occurrence an integer of 0-3; q2 iseach independently at each occurrence an integer of 0-3; r2 is eachindependently at each occurrence an integer of 0-3; R^(e) is eachindependently at each occurrence —Y—SiR⁸⁵ _(n2)R⁸⁶ _(n2); R^(f) is eachindependently at each occurrence a hydrogen atom or a lower alkyl group;k2 is each independently at each occurrence an integer of 0-3; l2 iseach independently at each occurrence an integer of 0-3; and m2 is eachindependently at each occurrence an integer of 0-3; in formulae (D1) and(D2), at least one q2 is 2 or 3, or at least one l2 is 2 or 3; and (2) afluorine containing oil of the general formula (O):Rf¹-PFPE′-Rf²  (O) wherein: Rf¹ is each independently at each occurrencea C₁₋₁₆ alkyl group which may be substituted by one or more fluorineatoms; Rf² is a C₁₋₁₆ alkyl group which may be substituted by one ormore fluorine atoms, a fluorine atom or a hydrogen atom; PFPE′ is—(OC₄F₈)_(a′)—(OC₃F₆)_(b′)—(OC₂F₄)_(c′)—(OCF₂)_(d′)—; a′, b′, c′ and d′are each independently an integer of 0 or more and 300 or less, the sumof a′, b′, c′ and d′ is at least 1, and the occurrence order of therespective repeating units in parentheses with the subscript a′, b′, c′or d′ is not limited in the formula, wherein a content of the fluorinecontaining oil having a molecular weight of 2.0 or more times higherthan the number average molecular weight of the fluorine-containing oilamong the fluorine containing oil of the formula (O) is 10 mol % orless.
 2. The surface-treating agent according to claim 1 wherein thecontent of the fluorine containing oil having a molecular weight of 2.0or more times higher than the number average molecular weight of thefluorine-containing oil among the fluorine containing oil of the formula(O) is 5 mol % or less.
 3. The surface-treating agent according to claim1 wherein a content of the fluorine containing oil having a molecularweight of 1.8 or more times higher than the number average molecularweight of the fluorine-containing oil among the fluorine containing oilof the formula (O) is 10 mol % or less.
 4. The surface-treating agentaccording to claim 3 wherein the content of the fluorine containing oilhaving a molecular weight of 1.8 or more times higher than the numberaverage molecular weight of the fluorine-containing oil among thefluorine containing oil of the formula (O) is 5 mol % or less.
 5. Thesurface-treating agent according to claim 1 wherein a number averagemolecular weight of the fluorine containing oil is 1,500 or more and30,000 or less.
 6. The surface-treating agent according to claim 5wherein the number average molecular weight of the fluorine containingoil is 2,000 or more and 10,000 or less.
 7. A surface-treating agentcomprising (1) at least one perfluoro(poly)ether group containing silanecompound of any of the formulae (A1), (A2), (B1), (B2), (C1), (C2), (D1)and (D2):

wherein: PFPE is each independently at each occurrence a group of theformula:—(OC₄F)_(a)—(OC₃F₆)_(b)—(OC₂F₄)_(c)—(OCF₂)_(d)— wherein a, b, c and dare each independently an integer of 0-200, the sum of a, b, c and d isat least one, and the occurrence order of the respective repeating unitsin parentheses with the subscript a, b, c or d is not limited in theformula; Rf is each independently at each occurrence an alkyl grouphaving 1-16 carbon atoms which may be substituted by one or morefluorine atoms; R¹ is each independently at each occurrence a hydroxylgroup or a hydrolyzable group; R² is each independently at eachoccurrence a hydrogen atom or an alkyl group having 1-22 carbon atoms;R¹¹ is each independently at each occurrence a hydrogen atom or ahalogen atom; R¹² is each independently at each occurrence a hydrogenatom or a lower alkyl group; n1 is, independently per a unit(—SiR_(n1)R² _(3−n1)), an integer of 0-3; at least one n1 is an integerof 1-3 in the formulae (A1), (A2), (B1) and (B2); X¹ is eachindependently a single bond or a 2-10 valent organic group; X² is eachindependently at each occurrence a single bond or a divalent organicgroup; t is each independently at each occurrence an integer of 1-10; αis each independently an integer of 1-9; α′ is each independently aninteger of 1-9; X⁵ is each independently a single bond or a 2-10 valentorganic group; β is each independently an integer of 1-9; β′ is eachindependently an integer of 1-9; X⁷ is each independently a single bondor a 2-10 valent organic group; γ is each independently an integer of1-9; γ′ is each independently an integer of 1-9; R^(a) is eachindependently at each occurrence —Z—SiR⁷¹ _(p1)R⁷² _(q1)R⁷³ _(r1); Z¹ iseach independently at each occurrence an oxygen atom or a divalentorganic group; R⁷¹ is each independently at each occurrence R^(a′);R^(a′) has the same definition as that of R^(a); in R^(a), the number ofSi atoms which are straightly linked via the Z¹ group is up to five; R⁷²is each independently at each occurrence a hydroxyl group or ahydrolyzable group; R^(n) is each independently at each occurrence ahydrogen atom or a lower alkyl group; p1 is each independently at eachoccurrence an integer of 0-3; q1 is each independently at eachoccurrence an integer of 0-3; r1 is each independently at eachoccurrence an integer of 0-3; at least one q1 is an integer of 1-3 inthe formula (C1) and (C2); R^(b) is each independently at eachoccurrence a hydroxyl group or a hydrolyzable group; R^(c) is eachindependently at each occurrence a hydrogen atom or a lower alkyl group;k1 is each independently at each occurrence an integer of 1-3; l1 iseach independently at each occurrence an integer of 0-2; m1 is eachindependently at each occurrence an integer of 0-2; the sum of k1, l1and m1 is 3 in each unit in parentheses with the subscript γ; X⁹ is eachindependently a single bond or a 2-10 valent organic group; δ is eachindependently an integer of 1-9; δ′ is each independently an integer of1-9; R^(d) is each independently at each occurrence —Z—CR⁸¹ _(p2)R⁸²_(q2)R⁸³ _(r2); Z² is each independently at each occurrence an oxygenatom or a divalent organic group; R⁸¹ is each independently at eachoccurrence R^(d′); R^(d′) has the same definition as that of R^(d); inR^(d), the number of C atoms which are straightly linked via the Z²group is up to five; R⁸ is each independently at each occurrence—Y—SiR⁸⁵ _(n2)R⁸⁶ _(3−n2); Y is each independently at each occurrence adivalent organic group; R⁸⁵ is each independently at each occurrence ahydroxyl group or a hydrolyzable group; R⁸⁶ is each independently ateach occurrence a hydrogen atom or a lower alkyl group; n2 is an integerof 1-3 independently per unit (—Y—SiR⁸⁵ _(n2)R⁸⁶ _(3−n2)); in formulae(D1) and (D2), at least one n2 is an integer of 1-3; R⁸³ is eachindependently at each occurrence a hydrogen atom or a lower alkyl group;p2 is each independently at each occurrence an integer of 0-3; q2 iseach independently at each occurrence an integer of 0-3; r2 is eachindependently at each occurrence an integer of 0-3; R^(e) is eachindependently at each occurrence —Y—SiR⁸⁵ _(n2)R⁸⁶ _(n2); R^(f) is eachindependently at each occurrence a hydrogen atom or a lower alkyl group;k2 is each independently at each occurrence an integer of 0-3; l2 iseach independently at each occurrence an integer of 0-3; and m2 is eachindependently at each occurrence an integer of 0-3; in formulae (D1) and(D2), at least one q2 is 2 or 3, or at least one l2 is 2 or 3; and (2) afluorine containing oil of the general formula (O):Rf¹-PFPE′-Rf²  (O) wherein: Rf¹ is each independently at each occurrencea C₁₋₁₆ alkyl group which may be substituted by one or more fluorineatoms; Rf² is a C₁₋₁₆ alkyl group which may be substituted by one ormore fluorine atoms, a fluorine atom or a hydrogen atom; PFPE′ is—(OC₄F₈)_(a′)—(OC₃F₆)_(b′)—(OC₂F₄)_(c′)—(OCF₂)_(d′)—; a′, b′, c′ and d′are each independently an integer of 0 or more and 300 or less, the sumof a′, b′, c′ and d′ is at least 1, and the occurrence order of therespective repeating units in parentheses with the subscript a′, b′, c′or d′ is not limited in the formula, wherein a content of the fluorinecontaining oil having a molecular weight of 5,000 or more in thefluorine containing oil of the formula (O) is 10 mol % or less.
 8. Thesurface-treating agent according to claim 7 wherein the content of thefluorine containing oil having a molecular weight of 5,000 or more inthe fluorine containing oil of the formula (O) is 5 mol % or less. 9.The surface-treating agent according to claim 1 wherein a dispersity ofthe fluorine containing oil is 1.00 or more and 1.20 or less.
 10. Thesurface-treating agent according to claim 9 wherein the dispersity ofthe fluorine containing oil is 1.00 or more and 1.10 or less.
 11. Thesurface-treating agent according to claim 1 wherein the number averagemolecular weight of the fluorine containing oil is 1,500 or more and5,500 or less.
 12. The surface-treating agent according to claim 1wherein the fluorine containing oil is one or more compounds of theformula (O1) or (O2):R²¹—(OCF₂CF₂CF₂)_(b″)—R²²  (O1)R²¹—(OCF₂CF₂CF₂CF₂)_(a″)—(OCF₂CF₂CF₂)_(b″)—(OCF₂CF₂)_(c″)—(OCF₂)_(d″)—R²²  (O2)R²¹ is an alkyl group having 1-16 carbon atoms which may be substitutedby one or more fluorine atoms; R²² is an alkyl group having 1-16 carbonatoms which may be substituted by one or more fluorine atoms, a fluorineatom or a hydrogen atom; in the formula (O1), b″ is an integer of 1 ormore and 100 or less; in the formula (O2), a″ and b″ are eachindependently an integer of 0 or more and 30 or less, and c″ and d″ areeach independently an integer of 1 or more and 300 or less; and theoccurrence order of the respective repeating units in parentheses withthe subscript a″, b″, c″ or d″ is not limited in the formula.
 13. Thesurface-treating agent according to claim 12 wherein the fluorinecontaining oil is one or more fluorine containing oils of the formula(O2), and the number average molecular weight of the fluorine containingoil is 1,500-5,500.
 14. The surface-treating agent according to a claim1 wherein Rf is a perfluoroalkyl group having 1-16 carbon atoms.
 15. Thesurface-treating agent according to claim 1 wherein PFPE is a group ofany of the following formulas (i) to (iv):—(OCF₂CF₂CF₂)_(b)  (i) wherein b is an integer of 1-200;—(OCF(CF₃)CF₂)_(b)—  (ii) wherein b is an integer of 1-200;—(OCF₂CF₂CF₂CF₂)_(a)—(OCF₂CF₂CF₂)_(b)—(OCF₂CF₂)_(c)—(OCF₂)_(d)—  (iii)wherein a and b are each independently 0 or an integer of 1-30, c and dare each independently an integer of 1-200, and the occurrence order ofthe respective repeating units in parentheses with the subscript a, b, cor d is not limited in the formula; or—(R⁷—R⁸)_(f)—  (iv) wherein R⁷ is OCF₂ or OC₂F₄, R⁸ is a group selectedfrom OC₂F₄, OC₃F₆ and OC₄F₈; and f is an integer of 2-100.
 16. Thesurface-treating agent according to claim 1 wherein X¹, X⁵, X⁷ and X⁹are each independently a 2-4 valent organic group, α, β, γ and δ areeach independently 1-3, and α′, β′, γ′ and δ′ are
 1. 17. Thesurface-treating agent according to claim 1 wherein X¹, X⁵, X⁷ and X⁹are each independently a 2 valent organic group, α, β, γ and δ are 1,and α′, β′, γ′ and δ′ are
 1. 18. The surface-treating agent according toclaim 17 wherein X¹, X⁵, X⁷ and X⁹ are each independently—(R³¹)_(p′)—(X^(a))_(q′)— wherein: R³¹ is each independently a singlebond, —(CH₂)_(s′)— (wherein s′ is an integer of 1-20) or a o-, m- orp-phenylene group; X^(a) is —(X^(b))_(l′)— wherein l′ is an integer of1-10; X^(b) is each independently at each occurrence selected from thegroup consisting of —O—, —S—, an o-, m- or p-phenylene group, —C(O)O—,—Si(R³³)₂—, —(Si(R³³)₂O)_(m′)—Si(R³³)₂— (wherein m′ is an integer of1-100), —CONR³⁴—, —O—CONR³⁴—, —NR³⁴— and —(CH₂)_(n′)— (wherein n′ is aninteger of 1-20); R³³ is each independently at each occurrence a phenylgroup, a C₁₋₆ alkyl group or a C₁₋₆ alkoxy group; R³⁴ is eachindependently at each occurrence a hydrogen atom, a phenyl group or aC₁₋₆ alkyl group; p′ is 0, 1 or 2; q′ is 0 or 1; at least one of p′ andq′ is 1, the occurrence order of the respective repeating units inparentheses with the subscript p′ or q′ is not limited in the formula;and R³¹ and X^(a) is may be substituted with one or more substituentsselected from a fluorine atom, a C₁₋₃ alkyl group and a C₁₋₃ fluoroalkylgroup.
 19. The surface-treating agent according to claim 1 wherein X¹,X⁵, X⁷ and X⁹ are each independently selected from the group consistingof: —CH₂O(CH₂)₂—, —CH₂O(CH₂)₃—, —CH₂O(CH₂)₆—,—CH₂O(CH₂)₃Si(CH₃)₂OSi(CH₃)₂(CH₂)₂—,—CH₂O(CH₂)₃Si(CH₃)₂OSi(CH₃)₂OSi(CH₃)₂(CH₂)₂—,—CH₂O(CH₂)₃Si(CH₃)₂O(Si(CH₃)₂O)₂Si(CH₃)₂(CH₂)₂—,—CH₂O(CH₂)₃Si(CH₃)₂O(Si(CH₃)₂O)₃Si(CH₃)₂(CH₂)₂—,—CH₂O(CH₂)₃Si(CH₃)₂O(Si(CH₃)₂O)₁₀Si(CH₃)₂(CH₂)₂—,—CH₂O(CH₂)₃Si(CH₃)₂O(Si(CH₃)₂O)₂₀Si(CH₃)₂(CH₂)₂—, —CH₂OCF₂CHFOCF₂—,—CH₂OCF₂CHFOCF₂CF₂—, —CH₂OCF₂CHFOCF₂CF₂CF₂—, —CH₂OCH₂CF₂CF₂OCF₂—,—CH₂OCH₂CF₂CF₂OCF₂CF₂—, —CH₂OCH₂CF₂CF₂OCF₂CF₂CF₂—,—CH₂OCH₂CF₂CF₂OCF(CF₃)CF₂OCF₂—, —CH₂OCH₂CF₂CF₂OCF(CF₃)CF₂OCF₂CF₂—,—CH₂OCH₂CF₂CF₂OCF(CF₃)CF₂OCF₂CF₂CF₂—, —CH₂OCH₂CHFCF₂OCF₂—,—CH₂OCH₂CHFCF₂OCF₂CF₂—, —CH₂OCH₂CHFCF₂OCF₂CF₂CF₂—,—CH₂OCH₂CHFCF₂OCF(CF₃)CF₂OCF₂—, —CH₂OCH₂CHFCF₂OCF(CF₃)CF₂OCF₂CF₂—,—CH₂OCH₂CHFCF₂OCF(CF₃)CF₂OCF₂CF₂CF₂——CH₂OCH₂(CH₂)₇CH₂Si(OCH₃)₂OSi(OCH₃)₂(CH₂)₂Si(OCH₃)₂OSi(OCH₃)₂(CH₂)₂—,—CH₂OCH₂CH₂CH₂Si(OCH₃)₂OSi(OCH₃)₂(CH₂)₃—,—CH₂OCH₂CH₂CH₂Si(OCH₂CH₃)₂OSi(OCH₂CH₃)₂(CH₂)₃—,—CH₂OCH₂CH₂CH₂Si(OCH₃)₂OSi(OCH₃)₂(CH₂)₂—,—CH₂OCH₂CH₂CH₂Si(OCH₂CH₃)₂OSi(OCH₂CH₃)₂(CH₂)₂—, —(CH₂)₂—, —(CH₂)₃—,—(CH₂)₄—, —(CH₂)₅—, —(CH₂)₆—, —(CH₂)₂—Si(CH₃)₂—(CH₂)₂— —CONH—(CH₂)—,—CONH—(CH₂)₂—, —CONH—(CH₂)₃—, —CON(CH₃)—(CH₂)₃—, —CON(Ph)-(CH₂)₃—wherein Ph is a phenyl group, —CONH—(CH₂)₆—, —CON(CH₃)—(CH₂)₆—,—CON(Ph)-(CH₂)₆— wherein Ph is a phenyl group, —CONH—(CH₂)₂NH(CH₂)₃—,—CONH—(CH₂)₆NH(CH₂)₃—, —CH₂O—CONH—(CH₂)₃—, —CH₂O—CONH—(CH₂)₆—,—S—(CH₂)₃—, —(CH₂)₂S(CH₂)₃—, —CONH—(CH₂)₃Si(CH₃)₂OSi(CH₃)₂(CH₂)₂—,—CONH—(CH₂)₃Si(CH₃)₂OSi(CH₃)₂OSi(CH₃)₂(CH₂)₂—,—CONH—(CH₂)₃Si(CH₃)₂O(Si(CH₃)₂O)₂Si(CH₃)₂(CH₂)₂—,—CONH—(CH₂)₃Si(CH₃)₂O(Si(CH₃)₂O)₃Si(CH₃)₂(CH₂)₂—,—CONH—(CH₂)₃Si(CH₃)₂O(Si(CH₃)₂O)₁₀Si(CH₃)₂(CH₂)₂—,—CONH—(CH₂)₃Si(CH₃)₂O(Si(CH₃)₂O)₂₀Si(CH₃)₂(CH₂)₂— —C(O)O—(CH₂)₃—,—C(O)O—(CH₂)₆—, —CH₂—O—(CH₂)₃—Si(CH₃)₂—(CH₂)₂—Si(CH₃)₂—(CH₂)₂—,—CH₂—O—(CH₂)₃—Si(CH₃)₂—(CH₂)₂—Si(CH₃)₂—CH(CH₃)—,—CH₂—O—(CH₂)₃—Si(CH₃)₂—(CH₂)₂—Si(CH₃)₂—(CH₂)₃—,—CH₂—O—(CH₂)₃—Si(CH₃)₂—(CH₂)₂—Si(CH₃)₂—CH(CH₃)—CH₂—, —OCH₂—, —O(CH₂)₃—,—OCFHCF₂—,


20. The surface-treating agent according to claim 1 wherein X¹ is—O—CFR¹³—(CF₂)_(e)—, R¹³ is a fluorine atom or a lower fluoroalkylgroup, and e is 0 or
 1. 21. The surface-treating agent according toclaim 1 wherein X² is —(CH₂)_(s)—, and s is an integer of 0-2.
 22. Thesurface-treating agent according to claim 1 wherein k1 is 3, and q1 is 3in R^(a).
 23. The surface-treating agent according to claim 1 wherein l2is 3, and n2 is
 3. 24. The surface-treating agent according to claim 1wherein Y is a C₁₋₆ alkylene group, —(CH₂)_(g′)—O—(CH₂)_(h′)— (whereing′ is an integer of 0-6, and h′ is an integer of 0-6), or-phenylene-(CH₂)_(i′)— (wherein i′ is an integer of 0-6).
 25. Thesurface-treating agent according to claim 1 wherein X¹, X⁵, X⁷ and X⁹are each independently a 3-10 valent organic group.
 26. Thesurface-treating agent according to claim 25 wherein X¹, X⁵, X⁷ and X⁹are each independently selected from the group consisting of:

wherein in each group, at least one of T is the following group attachedto PFPE in the formulae (A1), (A2), (B1), (B2), (C1), (C2), (D1) and(D2): —CH₂O(CH₂)₂—, —CH₂O(CH₂)₃—, —CF₂O(CH₂)₃—, —(CH₂)₂—, —(CH₂)₃—,—(CH₂)₄—, —CONH—(CH₂)—, —CONH—(CH₂)₂—, —CONH—(CH₂)₃—, —CON(CH₃)—(CH₂)₃—,—CON(Ph)-(CH₂)₃— wherein Ph is a phenyl group, and

at least one of the other T is —(CH₂)_(n)— (wherein n is an integer of2-6) attached to the carbon atom or the Si atom in the formulae (A1),(A2), (B1), (B2), (C1), (C2), (D1) and (D2), and if present, the othersT are each independently a methyl group, a phenyl group, a alkoxy having1-6 carbon atoms, or a radical scavenger group or an ultraviolet rayabsorbing group, R⁴¹ is each independently a hydrogen atom, a phenylgroup, an alkoxy group having 1 to 6 carbon atoms or an alkyl grouphaving 1 to 6 carbon atoms, and R⁴² is each independently a hydrogenatom, a C₁₋₆ alkyl group or a C₁₋₆ alkoxy group.
 27. Thesurface-treating agent according to claim 1 wherein theperfluoro(poly)ether group containing silane compound is at least onecompound of any of the formulae (A1) and (A2).
 28. The surface-treatingagent according to claim 1 wherein the perfluoro(poly)ether groupcontaining silane compound is at least one compound of any of theformulae (B1) and (B2).
 29. The surface-treating agent according toclaim 1 wherein the perfluoro(poly)ether group containing silanecompound is at least one compound of any of the formulae (C1) and (C2).30. The surface-treating agent according to claim 1 wherein theperfluoro(poly)ether group containing silane compound is at least onecompound of any of the formulae (D1) and (D2).
 31. The surface-treatingagent according to claim 1 containing the fluorine containing oil at5-95% by weight with respect to the total of the perfluoro(poly)ethergroup containing silane compound and the fluorine containing oil. 32.The surface-treating agent according to claim 1 further comprising oneor more other components selected form a silicone oil and a catalyst.33. The surface-treating agent according to claim 1 further comprising asolvent.
 34. The surface-treating agent according to claim 1 which isused as an antifouling-coating agent or a water-proof coating agent. 35.The surface-treating agent according to claim 1 for vacuum deposition.36. A pellet comprising the surface-treating agent according to claim 1.37. An article comprising a base material and a layer which is formed ona surface of the base material from the surface-treating agent accordingto claim
 1. 38. The article having a haze value of 0.3 or less.
 39. Thearticle according to claim 37 wherein the base material is a glass or asapphire glass.
 40. The article according to claim 39 wherein the glassis a glass selected from the group consisting of a soda-lime glass, analkali aluminosilicate glass, a borosilicate glass, a non-alkalineglass, a crystal glass, and a quartz glass.
 41. The article according toclaim 37 wherein the article is an optical member.
 42. The articleaccording to claim 37 wherein the article is a display.
 43. Thesurface-treating agent according to claim 6 wherein the content of thefluorine containing oil in the surface treating agent is 5-90% by masswith respect to the total of the perfluoro(poly)ether group containingsilane compound and the fluorine containing oil.